Search NASA⌕ Search

SEARCH · Search NASA

Results for “nuclear forensic”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Investigation of potential polyatomic interferences on uranium isotope ratio measurements for the LS-APGD-Orbitrap MS system

The determination of actinide (e.g., U and Pu) content and isotopics is of importance to the nuclear forensics and safeguards communities. However, in the analysis of environmental samples, such as those collected by the International Atomic Energy Agency, uranium measurements can be complicated by isobaric interferences from polyatomic variants of heavy elements (e.g., Pb). This leads to complex, time-consuming sample manipulations (i.e., separations) before determining isotope ratios. An alternative strategy to sample pretreatment is to use high-resolution mass spectrometric platforms during the analysis to fully resolve the uranium isotopes from potential polyatomic interferences, negating the need for prior chemical separation. The liquid sampling - atmospheric pressure glow discharge (LS-APGD) coupled with an Orbitrap mass spectrometer provides a high-resolution (>70,000 m/Δm at m/z 200) inorganic mass spectrometry platform. Further, as a demonstration of the power of this instrumental platform, and indeed, the high-resolution approach in general, uranium isotope ratios were determined in the presence of elemental impurities (e.g., Pb, Pt, Ta, W) commonly encountered with environmental sample swipe analysis, without any prior treatment. Even at elemental impurity concentrations of 1000–5000× relative to uranium, no interference was observed with the 235 U or 238 U signal. In addition, the 235 U/ 238 U isotope ratio for the samples with the concomitants present are within 2 standard deviations of the values obtained without their addition, indicating that these impurities do not impact the determined uranium isotope ratio. These findings represent a significant first step in leveraging the high resolution of the LS-APGD-Orbitrap-MS to overcome isobaric and molecular interferences instead of relying on chemical separations.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Complete resolution across the neodymium/samarium isotopic envelope with a liquid sampling‐atmospheric pressure glow discharge — Orbitrap mass spectrometer

Rationale Nd and Sm isotope ratios play an important role in geological dating and as nuclear forensic signatures; however, the overlap of the respective 144, 148, 150 Nd/Sm isobars requires prior separations to be performed before analysis on typical MS platforms. The work presented here overcomes these isobaric interferences using ultrahigh‐mass resolution to alleviate interference without prior chemical separations. Methods A liquid sampling‐atmospheric pressure glow discharge ion source was coupled to a standard, QExactive Focus Orbitrap mass spectrometer, providing a mass resolution of ~80 k. A Spectroswiss FTMS booster X2 data acquisition package was used to collect extended transients, providing much higher mass resolution; ~230 k and ~600 k are employed here for Nd and Sm isotopes. Results While the standard Orbitrap resolution is far greater than typical “atomic” MS platforms, it was insufficient to alleviate all isobars. The use of a resolution of ~230 k resulted in baseline separation across the entire isotopic envelope for both Nd and Sm. Isotope ratios obtained from Nd:Sm mixtures using high‐resolution were equivalent to those found for individual‐element solutions, while isotope ratios obtained at a resolution of ~80 k (standard for the OEM data system) showed large deviations. Conclusions Use of ultrahigh‐resolution is an attractive alternative to extensive chemical separations to alleviate severe isobaric interferences. Sufficient mass resolution greatly reduces/eliminates the need for sample manipulations (separations) before analysis while reducing costs and total analysis times.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Progress Toward Fast Decay Energy Spectroscopy for Actinide Analysis

Decay energy spectroscopy (DES) is an increasingly popular technique for measuring isotopic composition of actinide samples for nuclear safeguards applications. Current approaches for actinide DES utilize milligram-scale external gold absorbers (> 0.1 nJ/K) that are integrated with actinide samples through mechanical kneading and are thermally connected to microcalorimeters using indium or gold wire bonds. This leads to relatively slow sensor rise time and, consequently, limits counting speed to a few counts per second. We are developing faster metallic magnetic calorimeter-based DES by integrating actinide samples with magnetic sensor materials. This reduces signal rise time and enables high counting speed while maintaining the ability to knead the radioactive source with the absorber. We have measured signal rise time of 0.7 μs with a 1.5 mg external gold absorber using this approach. Here, we also demonstrated online DES operation using an Ortec DSPEC 50, a commercially available data acquisition system developed for semiconductor detectors.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Analysis of an irradiated uranium sample for source attribution without chemical separation using microplasma ionization and ultrahigh resolution mass spectrometry

The use of element isotope ratios has great potential in not only determining the reactor type used to produce plutonium (Pu) but also in determining the burnup and the time since irradiation. While a powerful nuclear forensic technique, determining element isotope ratios is complicated by severe isobaric interferences when performed on typical inductively coupled plasma mass spectrometers. Such analyses require extensive chemical separations prior to analysis to alleviate the inter-elemental isobars. Ultrahigh mass resolution spectrometry provides a potential alternative, greatly reducing the complexity of sample preparation and turnaround times for these critical measurements. To demonstrate the power of the approach, a sample of irradiated, depleted uranium was analyzed with the liquid sampling—atmospheric pressure glow discharge ion source coupled to an Orbitrap mass spectrometer. The Orbitrap is augmented with an external data acquisition system, Spectroswiss’s FTMS-Booster X2T, allowing collection of extended ion transients, providing higher mass resolution. In using this approach, the 150 Sm/ 149 Sm and 152 Sm/ 149 Sm isotope ratios were found to be within 20% of predicted values without any chemical separations and without mass bias corrections. In addition, the 240 Pu/ 239 Pu isotope ratio was determined, free from the 238 UH + interferences common to the ICP-MS platforms, while at the same time allowing for the determination of U isotopic signatures. While these demonstrative results are from a single sample, the advantages of the microplasma/ultrahigh mass resolution approach to intra-element isotope ratio determinations are clear.

Fuel burnup↗
DOE OSTI2022

Determination of the 161 Tb half-life

There is significant interest in the use of terbium radioisotopes for applications in cancer therapy and diagnosis. Of these, 161 Tb, a medium energy beta- and prolific auger emitter, is being investigated as a potential alternative to 177 Lu. The higher proportion of conversion electron and Auger electron emissions, and variety of low-energy gammas make 161 Tb an attractive targeted theranostic. As a product of nuclear fission, 161 Tb is also of importance to nuclear forensics. The current evaluated half-life of 6.89(2) d has a standard uncertainty that contributes significantly to the standard uncertainty of decay calculated activity determination. Furthermore, the accuracy of this evaluated half-life has been called into question by measurements reported recently at the Institute of Radiation Physics (IRP), Switzerland. In this work, the half-life of 161 Tb was measured at three independent laboratories located in the United Kingdom and United States of America for a total of five determinations using three independent measurement techniques. In conclusion, the half-life determined for 161 Tb of 6.9637(29) d confirms the observed 1 % relative increase observed by IRP, though the reported half-lives in this work and at IRP are significantly different (ζ-score = 3.1).

half-life↗
DOE OSTI2023

Separation of rare earth element radioisotopes by reverse-phase high-speed counter-current chromatography

Analytical scale purification of rare earth element (REE) radioisotopes is typically accomplished using cation-exchange resins (e.g. AG 50W-X8) and high-performance liquid chromatography (HPLC). Despite the variety of improvements made since the development of this separation process in the 1950s, nearest neighbor separations remain a challenge, as does the issue of irreversible sample adsorption. Herein, we report a study that evaluates the potential of high-speed counter-current chromatography (HSCCC) as an alternative method for purifying REE elements, with specific reference to separations of fission product REE of interest to nuclear forensics. Complementary HSCCC REE separation experiments, one spiked with radiotracer and REE fission product activity, allowed for in depth analysis of resulting fractions from both an elemental (inductively coupled plasma atomic emission spectroscopy, ICP-AES) and radiological (gamma-ray spectrometry, beta counting) purity perspective. The highly reproducible nature of separation profiles generated from HSCCC instruments was leveraged to simplify work-up of samples containing radioisotopes. Subsequent radioanalytical evaluation revealed minimal carryover of Eu into neighboring Sm and Tb fractions (as indicated by presence of 150Eu), and trace contamination of the Tb fraction with Y (as indicated by presence of 91Y). Subtle differences in stationary phase retention across the two columns were reflected in significant variations in decontamination factors of duplicate parallel separations. Furthermore, these differences paired with obtained distribution of radioisotopes provided valuable insights into future improvements. Collectively, this study represents a significant step forward in development of HSCCC technology for task specific REE radioisotope purification.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2020

Preparation of 241 Am/ 243 Am gravimetric mixtures and development of Am isotopic and assay measurement techniques using thermal ionization mass spectrometry

Three gravimetric mixtures with 241 Am/ 243 Am isotope ratios at nominally 1:1, 20:1, and 200:1 were prepared for calibration of the thermal ionization mass spectrometer instruments used for americium isotopic and assay measurements by isotope dilution mass spectrometry. The total evaporation analytical technique was developed for high-accuracy and precision measurements of Am isotopic ratios. The technique was also applied to Am assay measurements using isotope dilution mass spectrometry. The Am isotope ratio and assay measurement techniques were utilized to characterize batches of americium oxide separated from plutonium materials in storage at Los Alamos National Laboratory in support of commercial use of 241 AmO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Analytical workflow dependence of experimental observables for uranium chemistries

In this work, we investigated how the sequencing of laboratory analytical methods used for chemical and morphological characterization influences analytical findings for particulate materials relevant to the nuclear fuel cycle, including UO2, U3O8, studtite (UO2O2·4H2O), and β-UO3, in the context of nuclear forensic analysis. Particles of each chemistry obtained from consistent production batches were exposed to Raman spectroscopy and scanning electron microscopy in varying orders to elucidate how the order in which the techniques are applied influences morphological and chemical observations as a function of particle size. The results indicate that particles from all four chemistries exposed to high-resolution electron imaging before Raman spectral analysis demonstrate optical vibrational spectral changes that reduce accurate interpretation of the underlying chemistry via Raman spectral analysis. We hypothesize that these changes are due to the thermal load of the electron beam imparted to the sample being unable to be dissipated by materials with poor thermal conduction properties. Results from this study will aid in determining best practices for forensic analysis procedures to reduce uncertainty in chemical determination of unknown particulate samples.

Manns, Rebecca [University of Nevada, Las Vegas]↗
DOE OSTI2025

Producing 236 U reference standards for Accelerator Mass Spectrometry at the University of Notre Dame

36 U is a rare isotope of uranium, naturally occurring in ores with an abundance of 236 U/ 238 U$<$ 1 x 10 -9 . The ability to detect it and make isotopic ratio measurements has applications ranging from nuclear forensics and nonproliferation to energy production and environmental protection. Currently, Accelerator Mass Spectrometry (AMS) is the only technique sensitive enough to accurately measure 236 U/ 238 U isotopic ratios as they exist in naturally occurring ores in the range of 236 U/ 238 U = 10 -12 $-$ 10 -9 . Some AMS facilities have demonstrated their capabilities to make these measurements. Historically, the lack of commercially available reference standards covering the range of naturally occurring 236 U/ 238 U abundances has necessitated the use of absolute measurements, notoriously difficult to do using AMS, resulting in increased uncertainties in measurements and a reliance on knowledge of systematic effects. To mitigate these issues, various AMS facilities have sought to develop their own reference standards. Using a reference standard prepared for other forms of mass spectrometry, a series of AMS suitable standards was created through dilution with low-background natural uranium. The techniques used to produce and characterize these materials as well as analysis of them using AMS will be discussed.

236U↗
DOE OSTI2025

Effects of grain size and porosity on cladding failure in high-burnup UO 2 : A sensitivity and uncertainty study

Isotopic taggants are being studied to aid in the provenance assessment of nuclear materials. However, these taggants must be selected such that they do not adversely affect fuel performance during normal operation or accident scenarios. Taggants are known to affect the fuel’s grain size and porosity. In the work described in this paper, the BISON fuel performance code was used to assess the potential effects of taggants (i.e., grain size and porosity) on fuel rod behavior and cladding failure during a high-burnup, large-break loss-of-coolant accident. Here, 281 individual fuel rods from the same reactor core were modeled for a sensitivity study, a parametric study, and uncertainty quantification. The cladding failure predictions often exhibited stochastic behavior. After additional study, it was found that the cladding failure model is highly sensitive to residual error inherent to numerical approximation solvers. Some strategies to mitigate this sensitivity are discussed. The study found no relationship between known taggant effects and cladding failure status. However, taggants were found to affect the time and location of failure in certain rods. In conclusion, future work to continue investigating and validating these findings is briefly discussed.

Doped UO 2↗
DOE OSTI2025

Development of chemometric models to classify solid-state U materials by micro-Raman spectroscopy

Discerning uranium (U) particles found in environmental sampling is of interest for monitoring the peaceful use of nuclear material. In this study, a soft independent modeling of class analogy (SIMCA) library was successfully developed for the classification of a four-class system consisting of α-U 3 O 8 , UO 2 , UO 2 (NO 3 ) 2 ·6H 2 O (UNH), and UO 2 O 2 ·4H 2 O (studtite) by Raman spectroscopy in the presence of matrix particulates and additional outliers. Spectral variability between numerous particles of each type revealed appreciable differences as a function of particle size with respect to hydration state and potential oxide phase within each class. Interclass variability was accounted for using both unsupervised and supervised chemometric models. The supervised SIMCA model displayed reasonable sensitivity for each U class and a high degree of specificity by returning whether a spectrum belonged to one class or not. This work demonstrates how Raman spectral features and chemometrics can be used to distinguish U materials from one another and from matrix materials such as flint clay. Combining the outlined chemometric approach with Raman mapping sequences could provide a rapid, nondestructive technique to characterize the chemical composition of a diverse collection of U compounds amid background samples for environmental sampling, nuclear forensics, and industrial applications.

Actinide↗
DOE OSTI2021

A new highly enriched 233 U reference material for improved simultaneous determination of uranium amount and isotope amount ratios in trace level samples

A highly-enriched 233 U reference material (>0.99987 n( 233 U)/n(U)) has been prepared and characterized for use as an isotope dilution mass spectrometry spike. An ion exchange separation was performed on 1 g of high purity 233 U to further reduce trace amounts of contaminant Pu in the material. The purified 233 U was then prepared as a master solution which was analyzed for molality of uranium by modified Davies and Gray titration. A portion of the master solution was quantitatively diluted and dispensed for reference material units. Selected units were analyzed for verification of uranium amount and to characterize uranium isotope amount ratios by multi-collector inductively couple plasma mass spectrometry. Furthermore, modelling of spike-corrected isotopic data show that the new spike will enable simultaneous measurements of uranium amount and isotope amount ratios with resulting uncertainties that are substantially less sensitive to over spiking than widely used 233 U certified reference materials.

233U↗
DOE OSTI2021

Isotopic Heterogeneity Imaged in a Uranium Fuel Pellet with Extreme Ultraviolet Laser Ablation and Ionization Time-of-Flight Mass Spectrometry

We use extreme ultraviolet laser ablation and ionization time-of-flight mass spectrometry (EUV TOF) to map uranium isotopic heterogeneity at the nanoscale (=100 nm). Using low-enriched uranium fuel pellets that were made by blending two isotopically distinct feedstocks, we show that EUV TOF can map the 235U/238U content in 100 nm-sized pixels. The two-dimensional (2D) isotope maps reveal U ratio variations in sub-microscale to =1 µm areas of the pellet that had not been fully exposed by microscale or bulk mass spectrometry analyses. Compared to the ratio distribution measured in a homogeneous U reference material, the ratios in the enriched pellet follow a ~3× wider distribution. These results indicate U heterogeneity in the fuel pellet from incomplete blending of the different source materials. EUV TOF results agree well with those obtained on the same enriched pellets by nanoscale secondary ionization mass spectrometry (NanoSIMS), which reveals a comparable U isotope ratio distribution at the same spatial scale. EUV TOF’s ability to assess and map isotopic heterogeneity at the nanoscale makes it a promising tool in fields such as nuclear forensics, geochemistry, and biology that could benefit from uncovering sub-microscale sources of chemical modifications.

Rush, Lydia A.↗
DOE OSTI2024

Assessing Gas-Phase Ion Reactivity of 50 Elements with NO and the Direct Application for 239 Pu in Complex Matrices Using ICP-MS/MS

Understanding the reactivity of metal cations with various reaction gases in ICP-MS/MS is important to determine the best gas to use for a given analyte/interference pair. In this study, nitric oxide (NO) was investigated as the reaction gas following previous experimental designs. The reactions with 50 elements were investigated to examine periodic trends in reactivity, validate theoretical modeling of reaction enthalpies as a method to screen reactant gases, and provide a baseline for potential in-line gas separation methods. ICP-MS/MS studies involving actinides are typically limited to Th, U and Pu, with analyses of Np and Am rarely reported in the literature. To date, only two previous methods have investigated the use of NO in ICP-MS/MS analyses. To showcase the utility of NO, a method was developed to measure 239 Pu in the presence of environmental matrix constituent and other actinides, like what could be expected from post-detonation debris, with no chemical separation prior to analysis. 239 Pu + was reacted to form 239 Pu 16 O + , eliminating interferences derived from the sample matrix by measuring 239 Pu + intensity at m/z = 255 ( 239 Pu 16 O + ). To validate NO for 238 U 1 H + interference removal in environmental matrices, standard reference materials were diluted to 1 mg per gram of solution and spiked to 0.05 pg/g of 239 Pu and 1 µg/g 238 U (Pu/U = 5 x 10 -8 ). Measured 239 Pu concentrations were within 6% of the spiked value. In conclusion, these results demonstrate that reliable 239 Pu measurements can be made at levels relevant to nuclear forensics without the need for extensive chemical matrix separation prior to analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 OSTI2020

Scaling Trivalent Actinide and Lanthanide Recovery by Diglycolamide Resin from Savannah River Site’s Mark-18A Targets

The Savannah River National Laboratory is implementing a separation flowsheet to recover rare isotopes and transplutonium elements from irradiated 242 Pu targets known as Mark-18A targets. The Mark-18A targets contain the United States’ supply of nonseparated 244 Pu, which has a wide range of applications from nuclear forensics to production of superheavy elements such as flerovium. The targets also contain hundreds of grams of heavy curium ( 246–248 Cm), which is used as a target material for 252 Cf production. This work investigates the use of diglycolomide resin (DGA Resin) to recover valuable trivalent actinides from the Mark-18A targets. Batch contact experiments were performed on a representative simulant to determine mass loadings. Furthermore, the resin showed an overall capacity of 11 mg/mL for a mixed metal matrix (Zr and La–Gd). Column experiments showed chromatographic separation with transition-metal breakthroughs occurring first followed by the lanthanide series La–Gd. The experiments showed that lanthanide breakthrough occurred after 11 mg/mL mass loading was reached on the column with the mixed metal matrix. A radiological column experiment with an in-line UV/vis cell was able to detect Nd breakthrough just prior to 241 Am breakthrough. Implementing an in-line UV/vis cell into full-scale Mark-18A target processing will be used to limit breakthrough of trivalent actinides recovered from the targets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Fractionation of Oxygen Isotopes in Uranium Oxides during Peroxide Precipitation and Dry Air Calcination

The interaction between uranium and oxygen-containing substrates is nearly ubiquitous within the nuclear fuel cycle. Given the well-known and predictable oxygen stable isotope compositions of atmospheric oxygen and meteoric waters around the world, the use of these isotopes as a potential geolocation or processing signature of uranium compounds has been of interest within the nuclear safeguards community. This study focuses on measuring the oxygen-stable isotope composition of synthetically produced uranium oxides to determine the mechanism and extent of fractionation during materials processing relevant to the nuclear fuel cycle. Here, metastudtite [UO 2 O 2 (H 2 O) 2 ] samples were first produced using water and hydrogen peroxide of a known oxygen isotope composition. This starting material was calcined in dry air at temperatures ranging from 300 °C to 1000 °C for 20 h producing oxides ranging in composition from UO 3 +x (0 ≤ x ≤ 0.5) to U 3 O 8 . In addition, calcinations between 500 and 800 °C were performed at different time intervals to evaluate the rate of isotopic equilibration. The δ 18 O values of water bound to metastudtite were measured by thermogravimetric analysis coupled to isotope ratio infrared spectroscopy (TGA–IRIS). A redesigned fluorination manifold was constructed at the University of Utah and was used to extract the bulk oxygen from precipitated and calcined products using bromine pentafluoride (BrF 5 ). Mineralization water on metastudtite (measured by TGA–IRIS) was closely associated with the aqueous environment of precipitation with a fractionation of +3.5 ± 0.6‰. In contrast, bulk oxygen from metastudtite (measured by fluorination and gas chromatography combined with isotope ratio mass spectrometry) was found to have an inconsistent fractionation with precipitation water. Samples calcined in dry air exhibited a wide range of oxygen isotope compositions which increased from δ 18 O = +1.4 ± 0.9‰ at 300 °C to +17.3 ± 0.9‰ at 1000 °C. This variation in δ 18 O values was a result of oxygen exchange with atmospheric O 2 and was found to be rapid at calcination temperatures greater than 600°C—with equilibration occurring in less than 2 h. These results provide insights into the incorporation and exchange of oxygen isotopes during precipitation and calcination processes comparable to those employed within the nuclear fuel cycle and establish a foundation for future investigations to build upon.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

A comparison of machine learning methods to classify radioactive elements using prompt-gamma-ray neutron activation data

The detection of illicit radiological materials is critical to establishing a robust second line of defence in nuclear security. Neutron-capture prompt-gamma activation analysis (PGAA) can be used to detect multiple radioactive materials across the entire Periodic Table. However, long detection times and a high rate of false positives pose a significant hindrance in the deployment of PGAA-based systems to identify the presence of illicit substances in nuclear forensics. In the present work, six different machine-learning algorithms were developed to classify radioactive elements based on the PGAA energy spectra. The model performance was evaluated using standard classification metrics and trend curves with an emphasis on comparing the effectiveness of algorithms that are best suited for classifying imbalanced datasets. We analyse the classification performance based on Precision, Recall, F1-score, Specificity, Confusion matrix, ROC-AUC curves, and Geometric Mean Score (GMS) measures. The tree-based algorithms (Decision Trees, Random Forest and AdaBoost) have consistently outperformed Support Vector Machine and K-Nearest Neighbours. Based on the results presented, AdaBoost is the preferred classifier to analyse data containing PGAA spectral information due to the high recall and minimal false negatives reported in the minority class.

97 MATHEMATICS AND COMPUTING↗