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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

International interlaboratory compilation of trace element concentrations in the CUP-2 uranium ore concentrate standard

Herein, a nuclear forensics investigation involving a uranium ore concentrate relies on accurate and precise analysis of impurities. Analytical data defensibility requires the use of reference materials as part of quality control. This study presents a compilation of trace element concentration results of the CUP-2 Uranium Ore Concentrate Standard measured by 11 different laboratories. The laboratories employed various dissolution methods, analytical preparation methods, and instrumental platforms. The data presented here contain concentrations of 66 impurities with up to 138 individual data points for each impurity. Consensus values have been assigned to each impurity following a statistical analysis of the data set.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2015

Improved precision and accuracy in quantifying plutonium isotope ratios by RIMS

Resonance ionization mass spectrometry (RIMS) holds the promise of rapid, isobar-free quantification of actinide isotope ratios in as-received materials (i.e. not chemically purified). Recent progress in achieving this potential using two Pu test materials is presented. RIMS measurements were conducted multiple times over a period of two months on two different Pu solutions deposited on metal surfaces. Measurements were bracketed with a Pu isotopic standard, and yielded absolute accuracies of the measured Pu-240/Pu-239 ratios of 0.7 and 0.58 %, with precisions (95 % confidence intervals) of 1.49 and 0.91 %. The minor isotope Pu-238 was also quantified despite the presence of a significant quantity of U-238 in the samples.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Tabletop soft x-ray absorption spectroscopy for molecular fingerprinting

For applications related to nuclear security, safeguards, and nonproliferation, it is often critical to know the molecular compositions of lanthanide- and actinide-containing samples. Spectroscopy is a widely used tool that looks at the interaction between light and matter: Different species absorb or emit light at unique wavelengths which act as signatures. However, there is a limited number of tools that can achieve high-sensitivity, accurate measurements of lanthanide and actinide molecular compositions. Candidate methods include mass spectrometry, which usually destroys at least part of the sample and requires complicated stoichiometry to guess the original sample’s molecular compositions; optical spectroscopies, which have great atomic but limited molecular sensitivities or other drawbacks which make sensing molecules difficult like limited light sources or strong absorption in the atmosphere; and nuclear spectroscopies (gamma, neutron) which also have limited sources and long (>minute) collection times. As such, the purpose of our research is to develop a new tool to better distinguish between subtle differences in molecules containing lanthanides and actinides. Soft x-ray spectroscopy is sensitive to molecular form and is minimally intrusive/nondestructive to the sample. However, soft x-ray light with sufficient brightness for spectroscopy is typically limited to user-facilities like synchrotrons or free electron lasers, where beamtimes are competitive, and work with radiological materials may be difficult or entirely prohibited. To overcome this issue, our Team has developed a custom tabletop laser-driven, soft x-ray light source which employs high harmonic generation (HHG). Soft x-ray spectroscopy can distinguish between subtly different molecules, in the spectral range which we need to study these heavy elements. A tabletop system provides an effective and affordable tool to find both the elemental and chemical specificity of lanthanide and samples. Creating a light source in the soft x-ray spectrum is difficult because these wavelengths in the range 5-20 nm (20-350 eV photon energies) only penetrate several 100s of nm in most solid materials and only reflect well in shallow, grazing incident angles. The results are applicable to nuclear forensics, because molecular fingerprinting of lanthanide and actinide samples can be used to back out the origin and processing method of nuclear materials (Skrodzki, et al.).

36 MATERIALS SCIENCE↗
DOE OSTI2013

Nuclear Forensics International Technical Working Group (ITWG): a collaboration of scientists, law enforcement officials, and regulators working to combat nuclear terrorism and proliferation

Founded in 1996 upon the initiative of the “Group of 8” governments (G8), the Nuclear Forensics International Technical Working Group (ITWG) is an ad hoc organization of official Nuclear Forensics practitioners (scientists, law enforcement, and regulators) that can be called upon to provide technical assistance to the global community in the event of a seizure of nuclear or radiological materials. The ITWG is supported by and is affiliated with nearly 40 countries and international partner organizations including the International Atomic Energy Agency (IAEA), EURATOM, INTERPOL, EUROPOL, and the United Nations Interregional Crime and Justice Research Institute (UNICRI) (Figure 1). Besides providing a network of nuclear forensics laboratories that are able to assist the global community during a nuclear smuggling event, the ITWG is also committed to the advancement of the science of nuclear forensic analysis, largely through participation in periodic table top and Collaborative Materials Exercises (CMXs). Exercise scenarios use “real world” samples with realistic forensics investigation time constraints and reporting requirements. These exercises are designed to promote best practices in the field and test, evaluate, and improve new technical capabilities, methods and techniques in order to advance the science of nuclear forensics. Past efforts to advance nuclear forensic science have also included scenarios that asked laboratories to adapt conventional forensics methods (e.g. DNA, fingerprints, tool marks, and document comparisons) for collecting and preserving evidence comingled with radioactive materials.

Schwantes, Jon M.↗
DOE OSTI2016

Guidance on Radiochronometry

Radiochronometry is the measurement of radioactive materials and their decay products to determine the “age” of the material. It differs from the practice of geochronology in that the materials (samples) are man-made, and in that the timespan of interest is confined to the nuclear era, i.e., since the discovery of fission in 1939. In radiochronometry, the “age” of the material ideally records the time when the sample was manufactured, or produced in the final form that is analyzed in the laboratory. It is an important predictive signature in a nuclear forensic investigation which can help in the attribution to a source. The calculation of this “age” can only be made if a model is invoked that allows simplification of the parent radionuclide to daughter isotope decay equation. The simplification required for this model is that the parent was purified completely from all traces of its daughter product at the time of sample preparation. Then, this “age” should be described as the “model age” from which a “model date” in the past can then be calculated. For this model date to represent the date of sample preparation, two other assumptions are required to be true. The first is that the material has remained a closed system since that time (i.e., that there has been no loss or gain of either parent or daughter), and the second is that the analyses are accurate.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Application of ATONA Amplifiers to the Measurement of Uranium Isotopic Ratios by Thermal Ionization Mass Spectrometry

Uranium isotopic composition can provide valuable information about the history and provenance of a nuclear material; therefore, uranium isotopic analyses are frequently made in the nuclear forensics, safeguards, and environmental monitoring communities. These measurements have always presented challenges due to the extreme variability in the relative abundance between the major ( 235 U, 238 U) and minor ( 233 U, 234 U, 236 U) isotopes of uranium. Here, the recently developed ATONA (Atto- to Nano-Amp) amplification system paired with Faraday cup detectors has a large dynamic range and low noise floor making it ideal for measuring uranium isotopic ratios in materials of both natural and anthropogenic origin. A wide variety of certified reference materials were analyzed to investigate the utility of the ATONA amplification system for determining uranium isotopic composition in samples ranging from depleted to highly enriched. The ATONA amplifiers provide nearly an order of magnitude improvement in external reproducibility over 10 11 Ω amplifiers when measuring the minor 234 U/ 238 U ratio in isotopically natural and depleted samples and when paired with a secondary electron multiplier can measure very low relative abundance uranium isotopes (i.e., 236 U).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Three-dimensional microstructural characterization of bulk plutonium and uranium metals using focused ion beam technique

Nuclear forensics requires accurate quantification of discriminating microstructural characteristics of the bulk nuclear material to identify its process history and provenance. Conventional metallographic preparation techniques for bulk plutonium (Pu) and uranium (U) metals are limited to providing information in two-dimension (2D) and do not allow for obtaining depth profile of the material. In this contribution, use of dual-beam focused ion-beam/scanning electron microscopy (FIB-SEM) to investigate the internal microstructure of bulk Pu and U metals is demonstrated. Our results demonstrate that the dual-beam methodology optimally elucidate microstructural features without preparation artifacts, and the three-dimensional (3D) characterization of inner microstructures can reveal salient microstructural features that cannot be observed from conventional metallographic techniques. As a result, examples are shown to demonstrate the benefit of FIB-SEM in improving microstructural characterization of microscopic inclusions, particularly with respect to nuclear forensics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2018

Flexible classification with spatial quantile comparison and novel statistical features applied to spent nuclear fuel analysis

Multivariate classification algorithms are a common tool in contemporary data science that have begun to be applied to nuclear forensic analyses. Using a multivariate generalization of quantile–quantile plots for comparing unknown statistical distributions, a new model-free multivariate classifier called the Quantile–Quantile Comparator has been developed and tested on the analysis of simulated irradiated nuclear fuel. A method to estimate the sample-specific probability of having made an incorrect classification decision by analyzing the distribution of quantile comparisons has been developed, and methods have been developed to analyze the partition of the known data library used to analyze unknown data. By analyzing this partition, the analyst may identify classes that are likely to be confused, identify test data that are inconsistent with the data library and return a “None-of-the-Above” classification decision, and optimize the class boundaries. In this paper, the development of these capabilities is described, and a case study using real experimental assay data collected from nuclear fuel extracted from the newly-released In conclusion, Spent Fuel Isotopic Composition Database to demonstrate the efficacy of these capabilities is presented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Dynamic analysis environment for nuclear forensic analyses

We report a Dynamic Analysis Environment (DAE) software package is introduced to facilitate group inclusion/exclusion method testing, evaluation and comparison for pre-detonation nuclear forensics applications. Employing DAE, the multivariate signatures of a questioned material can be compared to the signatures for different, known groups, enabling the linking of the questioned material to its potential process, location, or fabrication facility. Advantages of using DAE for group inclusion/exclusion include built-in query tools for retrieving data of interest from a database, the recording and documentation of all analysis steps, a clear visualization of the analysis steps intelligible to a non-expert, and the ability to integrate analysis tools developed in different programming languages. Two group inclusion/exclusion methods are implemented in DAE: principal component analysis, a parametric feature extraction method, and k nearest neighbors, a nonparametric pattern recognition method. Spent Fuel Isotopic Composition (SFCOMPO), an open source international database of isotopic compositions for spent nuclear fuels (SNF) from 14 reactors, is used to construct PCA and KNN models for known reactor groups, and 20 simulated SNF samples are utilized in evaluating the performance of these group inclusion/exclusion models. For all 20 simulated samples, PCA in conjunction with the Q statistic correctly excludes a large percentage of reactor groups and correctly includes the true reactor of origination. As a result, employing KNN, 14 of the 20 simulated samples are classified to their true reactor of origination.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2019

Preparation and calibration of a 231 Pa reference material

A 231 Pa reference material has been characterized for amount of protactinium. This reference material is primarily intended for calibration of 233 Pa tracers produced for 235 U– 231 Pa model age measurements associated with nuclear forensics and nuclear safeguards. Primary measurements for characterization were made by isotope dilution mass spectrometry of a purified 231 Pa solution using a 233 Pa isotopic spike. The spike was calibrated by allowing multiple aliquots of the 233 Pa spike solution to decay to 233 U and then measuring the ingrown 233 U by isotope dilution mass spectrometry using a certified uranium assay and isotopic standard as a reverse-spike. In conclusion, the new 231 Pa reference material will simplify calibration of the 233 Pa isotope dilution spikes, provide metrological traceability, and potentially reduce the overall measurement uncertainty of model ages.

231Pa↗
DOE OSTI2022

Collaborative Study for Certification of Trace Elements in Uranium Ore Concentrate CRMs UCLO-1, UCHI-1, and UPER-1

Trace impurity patterns are important nuclear forensic signatures in uranium ore concentrates (UOCs) and Certified Reference Materials (CRMs) are used to validate the analysis methods employed by end users. Herein, we discuss the certification campaign for three new UOC CRMs from the National Research Council Canada: UCLO-1 (https://doi.org/10.4224/crm.2020.uclo-1), UCHI-1 (https://doi.org/10.4224/crm.2020.uchi-1), and UPER-1 (https://doi.org/10.4224/crm.2020.uper-1). This study involved 15 laboratories from 10 countries, using sector-field and (triple) quadrupole inductively-coupled plasma mass spectrometry to analyze 64 trace element impurities. We discuss the importance of the acids used for sample digestion, difficulties analyzing in a high uranium matrix, and data combination and uncertainty evaluation for this large dataset.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Optical vibrational spectroscopic signatures of ammonium diuranate process parameters

Ammonium diuranate (ADU) is commonly encountered in the nuclear fuel cycle; however, previous investigations have shown that ADU is a complex mixture of distinct compounds. Moreover, production parameters are known to heavily influence the composition of the resulting ADU. Here, we examine four samples of ADU prepared at Oak Ridge National Laboratory (ORNL), and one sample of ADU made at Pacific Northwest National Laboratory (PNNL), with the goal of further characterizing and elucidating the effect of processing parameters such as stir rate, strike direction, and temperature on material composition. Process parameters during ADU precipitation at ORNL and PNNL were well documented, and we relate process variables to optical vibrational spectroscopic signatures observed using Raman and infrared (IR) spectroscopy. In addition, powder X-ray diffraction (PXRD) reveals differences in the solid-phase composition of ADU precipitates, but we find that the primary phase is similar to the uranyl oxyhydroxyhydrate mineral metaschoepite. Despite the significant phase contributions of a metaschoepite-like phase, spectroscopic evidence of both nitrate and ammonium are observed for all samples. To gain a more holistic understanding of spectroscopic features of process parameters in ADU, principal component analysis (PCA) is employed and results in observable signatures that relate to the stir rate used during synthesis. These results provide further information about the process-dependence of ADU precipitate composition.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Probing the thermal decomposition of plutonium (III) oxalate with IR and Raman spectroscopy, X-ray diffraction, and electron microscopy

The thermal decomposition of Pu(III) oxalate was analyzed by Raman microspectroscopy, infrared spectroscopy, scanning electron microscopy, and powder X-ray diffraction. These data show that crystalline Pu 2 (C 2 O 4 ) 3 •9H 2 O progressively loses water and oxalate ligands as it is heated, which leads to a decrease in long-range lattice ordering, though minimal changes are observed in gross crystalline morphology. The onset of PuO 2 formation was observed between 200 - 250 °C. Thermal decomposition of oxalate ligands leads to the formation of CO 2 and plutonium oxalate-carbonate moieties, which had not been observed in previously published thermogravimetric measurements of Pu(III) oxalate. Formation of plutonium oxalate-carbonate moieties is believed to be associated with a change in the plutonium oxidation state from 3+ to 4+, which occurs prior to PuO 2 formation. The data provided herein demonstrate the rich spectroscopic nature of a rather underexplored, and technologically relevant, plutonium system. Ideally these results will further future investigations into the Pu(III) oxalate system both experimentally and computationally.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Microstructural characterization of plutonium oxalate and oxide particles by three-dimensional focused ion beam tomography

Focused ion beam (FIB) tomography was used to characterize three-dimensional (3D) internal microstructures of plutonium oxalate and oxide particles. Sequential two-dimensional (2D) sectioning and imaging using FIB and 3D image reconstruction were used to elucidate and distinguish internal pore microstructure and distribution in plutonium oxide particles calcined from plutonium oxalate precipitates. The results show that the plutonium oxide particles have a significant increase in pore volume fraction while retaining the exterior morphological shape of the corresponding oxalate precipitates. This technique enables the examination of the internal structure of radioactive microparticles for nuclear forensics that is not available with conventional microscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Reproduction of melting behavior for vitrified hillforts based on amphibolite, granite, and basalt lithologies

Abstract European Bronze and Iron Age vitrified hillforts have been known since the 1700s, but archaeological interpretations regarding their function and use are still debated. We carried out a series of experiments to constrain conditions that led to the vitrification of the inner wall rocks in the hillfort at Broborg, Sweden. Potential source rocks were collected locally and heat treated in the laboratory, varying maximum temperature, cooling rate, and starting particle size. Crystalline and amorphous phases were quantified using X-ray diffraction both in situ, during heating and cooling, and ex situ, after heating and quenching. Textures, phases, and glass compositions obtained were compared with those for rock samples from the vitrified part of the wall, as well as with equilibrium crystallization calculations. ‘Dark glass’ and its associated minerals formed from amphibolite or dolerite rocks melted at 1000–1200 °C under reducing atmosphere then slow cooled. ‘Clear glass’ formed from non-equilibrium partial melting of feldspar in granitoid rocks. This study aids archaeological forensic investigation of vitrified hillforts and interpretation of source rock material by mapping mineralogical changes and glass production under various heating conditions.

42 ENGINEERING↗
DOE OSTI2023

Assessment of the quality of nuclear data for stable oxygen isotopes for Intentional Forensics applications

The Intentional Forensics (IF) project seeks to design a suite of tagging materials that can be used to unobtrusively “barcode” nuclear fuel. The idea being that, if the fuel leaves institutional controls and is later recovered, the “barcode” can be used to determine the provenance of the fuel. The IF project is investigating several schemes for this “barcode” and taggants with tailored isotopic compositions are once leading concept. Recently 18 O was suggested as a potential taggant [IF2023]. This report assesses the quality of 16,17,18 O evaluations in the ENDF/B-VIII.0 library [ENDF8.0]. In a neutron-rich environment such as a nuclear reactor, we are interested in two main processes – neutron scattering and neutron absorption (or capture). For the typical neutron energies encountered in a reactor, absorption is determined exclusively by the neutron radiative capture cross section (in which a neutron is absorbed, and the residual nucleus emits one or more gamma rays). The capture cross sections are described by and can be completely determined from R-matrix parameters in the ENDF evaluations. Therefore, it is sufficient to consider the quality of the neutron resonance part of these evaluations. Neutron scattering is determined mainly by the elastic scattering cross section which is very similar for all oxygen isotopes and is essentially constant until around 100 keV. The cross section varies from 3-4 barns, depending on the isotope, and 16 O has the largest elastic cross section of all isotopes. Therefore, we expect that significant amounts of 17 O and 18 O could diminish the moderating role of oxygen in fuel. We note that, in traditional power reactor, the hydrogen in the coolant water provides the vast majority of the moderation in the reactor, so the impact of 17 O and 18 O in any taggant would be minimal. At higher energies, neutron resonances start to play a role and the R-matrix parameters determine the cross sections. Fig. 1 shows the mass region near stable oxygen isotopes. As nuclei capture neutrons, they transmute into a different isotope, one unit to the right. In particular, 16 O transmutes to 17 O, 17 O transmutes to 18 O and 18 O transmutes to 19 O. 19 O, being unstable, beta decays in 27 s to 19 F. So, even if the 18 O neutron capture data is good, the fact that it transmutes into 19 F may be problematic and needs investigation. Fig. 2 from [NuDat] shows the thermal neutron capture cross sections for all nuclei in the ENDF/B-VII.1 library [ENDF7.1]. Clearly oxygen thermal capture values are quite small compared to other nuclei. Note, there is no 18 O evaluation in the ENDF/B-VII.1 library. In any event, given that neutron capture events lower the reactor reactivity and potentially induce chemical changes in the fuel, we will focus our attention on the capture part of the neutron resonances.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗