Nuclear Forensic Analysis Research Articles

Development of nuclear underground engineered test surrogates (NUGETS): preliminary composition study and production method

A method for formulation and production of a new variety of surrogate nuclear explosive melt debris (NEMD), Nuclear UnderGround Engineered Test Surrogates (NUGETS), based on detonation of a notional improvised nuclear device in an underground environment analogous to the Nevada National Security Site is presented. Extensive statistical analyses of precursory geochemical and geophysical characteristics are combined with an augmented surrogate debris cooling technique. Comparison of NUGETS formulation to those of other NEMD surrogates is reported. Application of NUGETS methodology to future studies in urban, underground, post-detonation technical nuclear forensic analysis is suggested.

Nuclear forensic signatures and structural analysis of uranyl oxalate, its products of thermal decomposition and Fe impurity dopant

Uranyl oxalate (UO2C2O4·xH2O) may exist at the back-end of the nuclear fuel cycle (NFC) as an intermediate in spent fuel reprocessing. The conditions used in aqueous reprocessing and thermal treatment can affect the physical and chemical properties of the material. Furthermore, trace impurities, such as Fe, may incorporate into the structure of these materials. In nuclear forensics, understanding relationships between processing variables aids in determination of provenance and processing history. In this study, the thermal decomposition of UO2C2O4·3H2O and phase analysis of its thermal products are examined. Their morphologies are discussed with respect to a matrix of solution processing conditions.

State of practice and emerging application of analytical techniques of nuclear forensic analysis: highlights from the 5th Collaborative Materials Exercise of the Nuclear Forensics International Technical Working Group (ITWG)

The Nuclear Forensics International Technical Working Group (ITWG), a community of nuclear forensic practitioners who respond to incidents involving nuclear and other radioactive material out of regulatory control, completed its fifth Collaborative Materials Exercise in 2017 (CMX-5). Forensic laboratories from 19 countries and one multinational organization aimed to advance nuclear forensic science and improve international cooperation in the event of a nuclear material security incident. In all, over 30 analytical techniques were utilized to investigate the samples, many techniques applying novel methods or offering improvements in turnaround time. An objective review of the state of practice and emerging application of analytical techniques of nuclear forensic analysis based upon this exercise is provided.

Multivariate Analysis Based on Geochemical, Isotopic, and Mineralogical Compositions of Uranium-Rich Samples

The chemical and isotopic (U, Pb, Sr) signatures for a suite (n = 23) of pristine (>80 wt. % UO2) and altered uraninite samples (>70–80 wt. % UO2) from various locations worldwide have been determined for the purpose of identifying potential fingerprints for nuclear forensic analysis. The characterization of the uraninite samples included determination of major, minor and trace element contents, Sr, Pb, and U isotopic compositions, and secondary mineral assemblages. Due to the multivariate approach adopted in this study, principal component analysis (PCA) has been employed to allow the direct comparison of multiple variable types. The PCA results indicate that the geological origin (sandstone, metamorphite, intrusive, granite and unconformity) of pristine uraninite can be readily identified utilizing various combinations of major and/or trace element concentrations with isotopic compositions.

Microscale Isotopic Variation in Uranium Fuel Pellets with Implications for Nuclear Forensics.

Until recently, the analysis and identification of nuclear fuel pellets in the context of a nuclear forensics investigation have been mainly focused on macroscopic characteristics, such as fuel pellet dimensions, uranium enrichment, and other reactor-specific features. Here, we report microscale isotopic heterogeneity observed in different fuel pellet fragments that were characterized in situ by nanoscale secondary ion mass spectrometry (NanoSIMS). The materials analyzed include fuel fragments obtained as part of the Collaborative Materials Exercise (CMX-4) organized by the Nuclear Forensics International Technical Working Group (ITWG), as well as a fuel pellet fragment from a commercial power reactor. Although the commercial fuel pellet showed a homogeneous 235U/238U ratio across the sample (within analytical error), NanoSIMS imaging of the CMX-4 fuel pellet fragments showed distinct microscale variations in the uranium isotopic composition. The average 235U enrichments were 2.2 and 2.9% for the two samples; however, the measured 235U/238U ratios varied between 0.0081 and 0.035 (0.79-3.3 atom % 235U) and between 0.0090 and 0.045 (0.89-4.3 atom % 235U). The measurement of 236U in one of the CMX-4 samples suggested the use of at least three uranium oxide powders of different isotopic compositions ("source terms") in the production of the pellets. These variations were not detected using the conventional bulk, macroscopic techniques applied to these materials. Our study highlights the importance of characterizing samples on the microscale for heterogeneities that would otherwise be overlooked and demonstrates the potential use of NanoSIMS in guiding further nuclear forensic analysis.

A response surface model of morphological changes in UO₂ and U₃O₈ following high temperature aging

Abstract The morphological changes that take place during the processing and storage of uranium oxides can provide valuable information on the processing history and storage conditions of an interdicted sample. In this study microstructural changes in two uranium oxides (UO2 and U3O8) due to changes in the aging conditions at elevated temperatures were quantified and modeled using a response surface methodology approach. This allowed the morphological changes to be used as a signature for the aging conditions for nuclear forensic analysis. A Box-Behnken design of experiment was developed using the independent variables: temperature from 100 to 400 °C, aging times from 2 to 48 h, and partial pressure of O 2 ( P O 2 ) ${{\rm{O}}_2}({{\rm{P}}_{{{\rm{O}}_{\rm{2}}}}})$ between ~0.0 kPa and 21.3 kPa. The design of experiment consisted of 54 samples per uranium oxide. Each aged sample was characterized using scanning electron microscopy (SEM) for image analysis. Utilizing the Morphological Analysis for Materials (MAMA) software package, particle size and shape were quantified using the acquired SEM images. Analysis of the particle attributes was completed using the Kolmogorov–Smirnov two sample test (K–S test) to determine if the particle size and shape distributions were statistically distinct. This data was then used to create response surfaces of the quantitative morphological changes based on the developed design of experiment. The U3O8 samples showed no statistically quantifiable differences due to the aging conditions. However, the UO2 samples had distinct morphological changes due to the experimental aging conditions. Specifically, the temperature factor had an increasing effect on the particle area, and a decreasing effect on particle circularity.

Nuclear recoil spectroscopy of levitated particles

We propose a new method for the detection and characterization of nuclear decay processes. Specifically, we describe how nuclear decay recoil can be observed within small particles levitated in an optical trap with high positional resolution. Precise measurements of the magnitude of each recoil as well as their rate of occurrence can provide accurate information about the isotopic composition of a radioactive sample. We expect that this new technique for nuclear material characterization will be especially useful in the area of nuclear forensic analysis.

What’s that yellow powder? A nuclear forensic case study

In this paper the utilization of three analytical chemistry techniques including gamma spectrometry, XRF, and ICP-MS/OES is described for performing nuclear forensic analyses on an unknown powder. We have demonstrated that each method was unique in providing specific material characteristics, yet they were also complementary for extracting useful nuclear forensic signatures. It is the integral effort of all three analytical chemistry tools in the nuclear forensic tool box that ultimately allowed us to reveal the identity of the unknown nuclear material as Nb2O5 mixed with ~ 9% HEU.

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 Spent Fuel Isotopic Composition Database to demonstrate the efficacy of these capabilities is presented.

Computational and experimental forensics characterization of weapons-grade plutonium produced in a thermal neutron environment

Abstract The growing nuclear threat has amplified the need for developing diverse and accurate nuclear forensics analysis techniques to strengthen nuclear security measures. The work presented here is part of a research effort focused on developing a methodology for reactor-type discrimination of weapons-grade plutonium. To verify the developed methodology, natural UO2 fuel samples were irradiated in a thermal neutron spectrum at the University of Missouri Research Reactor (MURR) and produced approximately 20 μg of weapons-grade plutonium test material. Radiation transport simulations of common thermal reactor types that can produce weapons-grade plutonium were performed, and the results are presented here. These simulations were needed to verify whether the plutonium produced in the natural UO2 fuel samples during the experimental irradiation at MURR was a suitable representative to plutonium produced in common thermal reactor types. Also presented are comparisons of fission product and plutonium concentrations obtained from computational simulations of the experimental irradiation at MURR to the nondestructive and destructive measurements of the irradiated natural UO2 fuel samples. Gamma spectroscopy measurements of radioactive fission products were mostly within 10%, mass spectroscopy measurements of the total plutonium mass were within 4%, and mass spectroscopy measurements of stable fission products were mostly within 5%.

Application of modern autoradiography to nuclear forensic analysis

Modern autoradiography techniques based on phosphorimaging technology using image plates (IPs) and digital scanning can identify heterogeneities in activity distributions and reveal material properties, serving to inform subsequent analyses. Here, we have adopted these advantages for applications in nuclear forensics, the technical analysis of radioactive or nuclear materials found outside of legal control to provide data related to provenance, production history, and trafficking route for the materials. IP autoradiography is a relatively simple, non-destructive method for sample characterization that records an image reflecting the relative intensity of alpha and beta emissions from a two-dimensional surface. Such data are complementary to information gathered from radiochemical characterization via bulk counting techniques, and can guide the application of other spatially resolved techniques such as scanning electron microscopy (SEM) and secondary ion mass spectrometry (SIMS). IP autoradiography can image large 2-dimenstional areas (up to 20×40cm), with relatively low detection limits for actinides and other radioactive nuclides, and sensitivity to a wide dynamic range (105) of activity density in a single image. Distributions of radioactivity in nuclear materials can be generated with a spatial resolution of approximately 50μm using IP autoradiography and digital scanning. While the finest grain silver halide films still provide the best possible resolution (down to ∼10μm), IP autoradiography has distinct practical advantages such as shorter exposure times, no chemical post-processing, reusability, rapid plate scanning, and automated image digitization. Sample preparation requirements are minimal, and the analytical method does not consume or alter the sample. These advantages make IP autoradiography ideal for routine screening of nuclear materials, and for the identification of areas of interest for subsequent micro-characterization methods. In this paper we present a summary of our setup, as modified for nuclear forensic sample analysis and related research, and provide examples of data from select samples from the nuclear fuel cycle and historical nuclear test debris.

Uranium assay and trace element analysis of the fourth collaborative material exercise samples by the modified Davies-Gray method and the ICP-MS/OES techniques

An international group of laboratories participating in CMX-4 subjected three samples to comparative nuclear forensic analysis using uranium assay and trace element analysis techniques to determine if the samples had similar or different origins. Uranium assay indicated that two pellet samples (ES-2 and ES-3) were nearly pure UO2 while the black powder sample ES-1 was primarily UO2 with UO3 and/or U3O8 forms present as impurities. Trace element analysis by five of the six participating laboratories reported molybdenum concentrations below 10 µg/g U in all of the exercise samples, suggesting the same likely facility of origin for all three samples.

LIBS development methodology for forensic nuclear materials analysis

Methodology development of LIBS coupled with chemometrics utilizing weak U-lines and spectral feature selection for rapid nuclear forensic analysis.

Spectroscopy and DFT studies of uranyl carbonate, rutherfordine, UO2CO3: a model for uranium transport, carbon dioxide sequestration, and seawater species

Several optical microprobe experiments of the anhydrous uranium carbonate—rutherfordine—are presented in this work and compared to periodic density functional theory results. Rutherfordine is the simplest uranyl carbonate and constitutes an ideal model system for the study of the rich uranium carbonate family relevant for environmental sustainability. Micro-Raman, micro-reflectance, and micro-photoluminescence (PL) spectroscopy studies have been carried out in situ on native, micrometer-sized crystals. The sensitivity of these techniques is sufficient to analyze minute amounts of samples in natural environments without using x-ray analysis. In addition, very intense micro-PL and micro-reflectance spectra that were not reported before add new results on the ground and excited states of this mineral. The optical gap value determined experimentally is found at about 2.6–2.8 eV. Optimized geometry, band structure, and phonon spectra have been calculated. The main vibrational lines are identified and predicted by this theoretical study. This work is pertinent for optical spectroscopy, for identification of uranyl species in various environmental settings, and for nuclear forensic analysis.

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

A cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) was developed in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. The method was applied to determine REE abundances in four uraninite (ideally UO2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondary uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K+ and Pb2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.

Production and characterization of synthetic urban nuclear melt glass

A method for producing realistic surrogate debris characteristic of those that would be expected to be found following a nuclear detonation in an urban environment is tested. The melt glass samples are benchmarked against synthetic trinitite via electron microscopy and X-ray diffractometry analysis. The surrogates produced proved to be similar to trinitite and synthetic nuclear melt glass, but showed differences indicative of the calculated precursor matrix for each city modeled. The synthetic debris produced may serve as a tool to advance and validate existing rapid nuclear forensic analysis methods.

Rapid Nuclear Forensics Analysis via Laser Based Microphotonic Techniques Coupled with Chemometrics

Nuclear forensics (NF) is an important tool for analysis and attribution of nuclear and radiological materials (NRM) in support of nuclear security. The critical challenge in NF currently is the lack of suitable microanalytical methodologies for direct, rapid and minimally-invasive detection and quantification of NF signatures. Microphotonic techniques can achieve this task particularly when the materials are of limited size and under concealed condition. The purpose of this paper is to demonstrate the combined potential of chemometrics enabled LIBS and laser Raman spectromicroscopy (LRS) for rapid NF analysis and attribution. Using LIBS, uranium lines at 385.464 nm, 385.957 nm and 386.592 nm were identified as NF signatures in uranium ore surrogates. A multivariate calibration strategy using artificial neural network was developed for quantification of trace uranium. Principal component analysis (PCA) of LIBS spectra achieved source attribution of the ores. LRS studies on UCl3, UO3(NO3)2.6H2O, UO2SO4.3H2O and UO3 in pellet state identified the bands associated with different uranium molecules as varying in the range of (840 to 867) ± 15 cm-1. Using this signature, we have demonstrated spectral imaging of uranium under concealed conditions.

A new thorium-229 reference material

A new reference material was characterized for 229Th molality and thorium isotope amount ratios. This reference material is intended for use in nuclear forensic analyses as an isotope dilution mass spectrometry spike. The reference material value and expanded uncertainty (k = 2) for the 229Th molality is (1.1498 ± 0.0016) × 10−10molg−1 solution. The value and expanded uncertainty (k = 2) for the n(230Th)/n(229Th) ratio is (5.18 ± 0.26) × 10−5 and the n(232Th)/n(229Th) ratio is (3.815 ± 0.092) × 10−4.

Trace element and U isotope analysis of uraninite and ore concentrate: Applications for nuclear forensic investigations

Uranium ore concentrate (UOC), is an important intermediate material in the nuclear fuel cycle. Trace element distributions in UOCs can be related to the geologic conditions in which the source uranium ore formed, and hence are characteristic for each deposit type. These chemical signatures can then potentially be used as an essential tool for nuclear forensic analysis of derivative radioactive materials. In this study, several samples of UOC and uraninite extracted from sandstone-hosted roll front deposits in the Powder River basin U province in Wyoming (USA) have been analyzed for their trace element abundances and U isotopic compositions. UOCs were analyzed both in solution mode-inductively coupled plasma mass spectrometry (SM-ICP-MS) subsequent bulk sample digestion, and at high-spatial resolution (10s of micron scale) using a laser ablation (LA)-ICP-MS technique. Comparison of trace elemental abundances obtained by SM- and LA-ICP-MS indicates corroborating results, with comparable chondrite-normalized rare earth element (REE) patterns; those obtained by LA-ICP-MS show a slightly larger variation in absolute elemental abundances compared with corresponding bulk sample digestions. U isotopic measurements for UOCs and uraninite were conducted by solution mode multi-collector (MC)-ICP-MS. 238U/235U, 235U/234U and 238U/234U ratios for uraninite and UOC overlap and confirm a lack of significant isotopic fractionation during the fabrication process. The results reported here assert the validity of analyzing UOC for source attribution purposes and simultaneously demonstrate that corroborating trace element signatures can be obtained with both LA and SM-ICP-MS analytical techniques for U-rich materials relevant to the nuclear fuel cycle. REE abundances and U isotopes did not fractionate during early ore processing of materials investigated in this study.

A novel nuclear forensic tool involving deposit type normalized rare earth element signatures

AbstractIdentifying the provenance of uranium‐rich materials is a critical objective of nuclear forensic analysis. Rare earth element (REE) distributions within uranium ores are well‐established forensic indicators, but quantifying and correlating trace element signatures for U ores to known deposits has thus far involved intricate statistical analyses. This study reports average chondrite normalized (CN)‐REE signatures for important U deposit types worldwide, which are then employed to evaluate U ore paragenesis using a simple linear regression analysis. This technique provides a straightforward method that can aid in determining the deposit type of U ores based on their REE abundances, and combined with other forensic indicators (e.g. radiogenic isotope signatures) can provide essential provenance information for nuclear materials.