Search NASA⌕ Search

SEARCH · Search NASA

Results for “forensic chemistry”

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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

An experimental and computational investigation of the structure and spectroscopic signatures of α -UO 3

α-UO 3 is a common intermediate compound found in the nuclear fuel cycle, yet the exact crystal structure of this material has long been debated. Inconsistent computational and experimental data in previous works has led to varying conclusions between authors. Furthermore, to ensure the validity of our results in this work, the structural and spectroscopic signatures of pure phase α-UO 3 are investigated using powder X-ray diffraction and optical vibrational spectroscopy (infrared and Raman). Rietveld refinement of powder X-ray diffraction data on pure phase α-UO 3 collected in this work allows us to propose an alteration to the currently accepted C2mm structure (a = 3.9705 Å, b = 6.8553 Å, c = 4.15955 Å, α = β = γ = 90°) for α-UO 3 with no uranyl [UO 2 2+ ] bonds. Raman spectra collected using two excitation wavelengths (two instruments using 532 nm and one 785 nm) are presented, and differences with recently published results are discussed. Infrared spectra from two instruments used here agree well with recently published results, but the spectral range encompassed in our data extends past what has been reported with modern techniques. Additionally, we provide tentative vibrational mode assignments based on density functional perturbation theory calculations and resulting phonon eigenvector visualizations. Unexpected features in the optical vibrational spectra of α-UO 3 are explained by unique features in the structure we present.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

CWMD Nuclear Forensics Quarterly Report

Analysis and evaluation of nuclear debris is a key component to identify forensic signatures in a post-detonation environment. Currently, methods exist and are practiced in obtaining signatures from post-detonation debris. However, efforts to reduce the timeline in obtaining signatures is continuous within nuclear forensics research and will be forwarded by this research. This education and research project will explore combined material chemistry and separations of radionuclides to provide actionable signatures in less time than standard methods. The research will use the phase distribution of radionuclides in debris to develop targeted and rapid dissolution methods. These dissolution methods will be coupled with microfluidics to achieve samples suitable for analysis within reduced timelines.

and nuclear chemistry↗
DOE OSTI2020

Uncovering Uranium Isotopic Heterogeneity of Fuel Pellets from the Fifth Collaborative Materials Exercise of the Nuclear Forensics International Technical Working Group

In 2017, the Nuclear Forensics International Technical Working Group (ITWG) organized their fifth 37 Collaborative Materials Exercise (CMX-5). The exercise samples were two uranium dioxide fuel pellets 38 manufactured from the same starting materials by different processes to have similar bulk isotopic 39 composition, but different spatial uranium isotopic distributions. Sets of identical materials were sent to 40 all participating laboratories, who then utilized their existing nuclear forensic capabilities to 41 independently analyse fuel pellets and identify similarities and differences of the materials’ 42 characteristics. The analytical methods used to probe the fuel pellets included ex situ, such as sectioning 43 or breaking up the pellets and analyzing dissolved pieces using inductively coupled plasma mass 44 spectrometry (ICP-MS), analyzing particles collected from intact or fragmented pellets by secondary ion 45 mass spectrometry (SIMS), as well as in situ methods, such as laser ablation coupled with ICP-MS, 46 autoradiography and nanoSIMS. In this paper we present the results of these independent analyses and 47 compare the capabilities of those nuclear forensic analytical methods to uncover details of the isotopic 48 heterogeneity of uranium fuel pellets.

Nuclear Forensic Analysis of Uranium Fuel Pellets,↗
DOE OSTI2020

Matrix-Assisted Ionization of Molecular Uranium Species

Matrix-assisted ionization (MAI) demonstrates high sensitivity for a variety of organic compounds; however, few studies have reported the application of MAI for the detection and characterization of inorganic analytes. Trace-level uranium analysis is important in the realms of nuclear forensics, nuclear safeguards, and environmental monitoring. Traditional mass spectrometry methods employed in these fields require combinations of extensive laboratory chemistry sample preparation and destructive ionization methods. There has been recent interest in exploring ambient mass spectrometry methods that enable timely sample analysis and higher sensitivity than what is attainable by field-portable radiation detectors. Rapid characterization of uranium at nanogram levels is demonstrated in this study using MAI techniques. Mass spectra were collected on an atmospheric pressure mass spectrometer for solutions of uranyl nitrate, uranyl chloride, uranyl acetate, and uranyl oxalate utilizing 3-nibrobenzonitrile as the ionization matrix. The uranyl complexes investigated were detectable, and the chemical speciation was preserved. Sample analysis was accomplished in a matter of seconds, and limits of detection of 5 ng of uranyl nitrate, 10 ng of uranyl oxalate, 100 ng of uranyl chloride, and 200 ng of uranyl acetate were achieved. The observed gas-phase speciation was similar to negative-ion electrospray ionization of uranyl compounds with notable differences. Six matrix-derived ions were detected in all negative-ion mass spectra, and some of these ions formed adducts with the uranyl analyte. Subsequent analysis of the matrix suggests that these molecules are not matrix contaminants and are instead created during the ionization process.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Flow Injection Electrochemical Quartz Crystal Microbalance with ICP-OES Detection: Electroprecipitation and Stripping of Lanthanum and Neodymium in a Flow Cell

We used an improved version of our hyphenated analysis technique, flow injection electrochemical quartz crystal microbalance (EQCM) with inductively coupled optical emission spectroscopy, to investigate the electroprecipitation of lanthanum and neodymium from flowing solutions. The improved version has two independent flow injection circuits, allowing different conditions for electrochemical precipitation (pH=4.3 or 2.6) and quick stripping (2% HNO3) with EQCM mass detection and ICP-OES elemental analysis. Lanthanum or neodymium ions in a 500 uL sample were injected into a carrier stream and deposited onto an EQCM housed in a micro flow cell, owing to a localized high-pH layer. The deposits are subsequently stripped from the electrode using HNO3 and analyzed downstream using an ICP-OES. We found that using acidic solutions without supporting electrolyte leads to an increase of the amount of lanthanum detected by 4-fold. The enhanced deposition can be attributed to enhanced mass transfer by migration. Furthermore, we showed that by applying chronopotentiometry, we can detect a change in the hydrogen evolution reaction mechanism that enables the precipitation of lanthanides on the surface of the electrode. Understanding and enhancing the deposition of lanthanides is relevant for elemental or isotopic detection in nuclear forensics.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

A Review of Nuclear Forensics: 2016-2020

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 United 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Synthetic diversity in the preparation of metallic uranium

Uranium metal is associated with several aspects of nuclear technology; it is used as fuel for research and power reactors, targets for medical isotope productions, explosive for nuclear weapons and precursors in synthetic chemistry. The study of uranium metal at the laboratory scale presents the opportunity to evaluate metallic nuclear fuels, develop new methods for metallic spent fuel reprocessing and advance the science relevant to nuclear forensics and medical isotope production. Since its first isolation in 1841, from the reaction of uranium chloride and potassium metal, uranium metal has been prepared by solid-state reactions and in solution by electrochemical, chemical and radiochemical methods. The present review summarizes the methods outlined above and describes the chemistry associated with each preparation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Impact of Controlled Storage Conditions on the Hydrolysis and Surface Morphology of Amorphous-UO 3

The hydration and morphological effects of amorphous (A)-UO 3 following storage under varying temperature and relative humidity have been investigated. This study provides valuable insight into U-oxide speciation following aging, the U-oxide quantitative morphological data set, and, overall, the characterization of nuclear material provenance. A-UO 3 was synthesized via the washed uranyl peroxide synthetic route and aged based on a 3-factor circumscribed central composite design of experiment. Target aging times include 2.57, 7.00, 14.0, 21.0, and 25.4 days, temperatures of 5.51, 15.0, 30.0, 45.0, and 54.5 °C, and relative humidities of 14.2, 30.0, 55.0, 80.0, and 95.8% were examined. Following aging, crystallographic changes were quantified via powder X-ray diffraction and an internal standard Rietveld refinement method was used to confirm the hydration of A-UO 3 to crystalline schoepite phases. The particle morphology from scanning electron microscopy images was quantified using both the Morphological Analysis of MAterials software and machine learning. Results from the machine learning were processed via agglomerative hierarchical clustering analysis to distinguish trends in morphological attributes from the aging study. Significantly hydrated samples were found to have a much larger, plate-like morphology in comparison to the unaged controls. Predictive modeling via a response surface methodology determined that while aging time, temperature, and relative humidity all have a quantifiable effect on A-UO 3 crystallographic and morphological changes, relative humidity has the most significant impact.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Detection and confirmation of fentanyls in high clay‐content soil by electron ionization gas chromatography‐mass spectrometry

Abstract Detection of illicit drugs in the environment, particularly in soils, often suggests the present or past location of a clandestine production center for these substances. Thus, development of efficient methods for the analysis and detection of these chemicals is of paramount importance in the field of chemical forensics. In this work, a method involving the extraction and retrospective confirmation of fentanyl, acetylfentanyl, thiofentanyl, and acetylthiofentanyl using trichloroethoxycarbonylation chemistry in a high clay‐content soil is presented. The soil was spiked separately with each fentanyl at two concentrations (1 and 10 μg/g) and their extraction accomplished using ethyl acetate and aqueous NH 4 OH (pH ~ 11.4) with extraction recoveries ranging from ~56% to 82% for the high‐concentration (10 μg/g) samples while ranging from ~68% to 83% for the low‐concentration (1 μg/g) samples. After their extraction, residues containing each fentanyl were reacted with 2,2,2‐trichloroethoxycarbonyl chloride (Troc‐Cl) to generate two unique and predictable products from each opioid that can be used to retrospectively confirm their presence and identity using EI‐GC‐MS. The method's limit of detection (MDL/LOD) for Troc‐norfentanyl and Troc‐noracetylfentanyl were estimated to be 29.4 and 31.8 ng/mL in the organic extracts. In addition, the method's limit of quantitation for Troc‐norfentanyl and Troc‐noracetylfentanyl were determined to be 88.2 and 95.5 ng/mL, respectively. Collectively, the results presented herein strengthen the use of chloroformate chemistry as an additional chemical tool to confirm the presence of these highly toxic and lethal substances in the environment.

Valdez, Carlos A.↗
DOE OSTI2024

Formation of Fully Stoichiometric, Oxidation-State Pure Neptunium and Plutonium Dioxides from Molecular Precursors

Amidate-based ligands (N-(tert-butyl)isobutyramide, ITA) bind κ 2 to form homoleptic, 8-coordinate complexes with tetravalent 237 Np (Np(ITA) 4 , 1-Np) and 242 Pu (Pu(ITA) 4 , 1-Pu). These compounds complete an isostructural series from Th, U–Pu and allow for the direct comparison between many of the early actinides with stable tetravalent oxidation states by nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction (SCXRD). The molecular precursors are subjected to controlled thermolysis under mild conditions with the exclusion of exogenous air and moisture, facilitating the removal of the volatile organic ligands and ligand byproducts. The preformed metal–oxygen bond in the precursor, as well as the metal oxidation state, are maintained through the decomposition, forming fully stoichiometric, oxidation-state pure NpO 2 and PuO 2 . Powder X-ray diffraction (PXRD), scanning transmission electron microscopy (STEM), and energy dispersive X-ray spectroscopy (EDS) elemental mapping supported the evaluation of these high-purity materials. This chemistry is applicable to a wide range of metals, including actinides, with accessible tetravalent oxidation states, and provides a consistent route to analytical standards of importance to the field of nuclear nonproliferation, forensics, and fundamental studies.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

PIXE – State of the Art, Systems, Challenges

Particle-induced X-ray emission (PIXE) is an analytical technique for elemental analysis in which a charged-particle beam (most commonly protons, but also alpha particles or heavier ions) ionizes inner-shell electrons in target atoms. When these vacancies are filled by outer-shell electrons, the atom emits characteristic X-rays (e.g., Kα, Kβ, L-series) whose energies are unique to each element. Measuring the X-ray spectrum therefore enables identification of the elements present and, with appropriate calibration and modeling, their concentration. PIXE provides rapid, simultaneous, quantitative multi-element detection with trace-level sensitivity for many mid- to high-Z elements, often with minimal sample preparation. It is widely used across materials science (thin films, alloys, corrosion), geology (mineral chemistry, provenance) and environmental monitoring (aerosols, particulates, soils); semiconductor contamination analysis (wafer surface/trace metals), cultural heritage (pigments, inks, archaeological artifacts) and forensics (gunshot residue, glass/pain), and biological/medical studies (tissue/biomaterial trace-element mapping).

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Single particle trace element analysis of uranium oxide standards with laser-induced breakdown spectroscopy

Femtosecond Laser-Induced Breakdown Spectroscopy (LIBS) was used to analyze over 1000 individual particles of uranium oxide trace element standard CRM124. Intra-granular analysis showed elemental concentrations were consistent across different surface locations on each uranium grain. However, inter-granular comparison revealed large heterogeneity between different grains of the same sample. By comparing the distribution of elemental concentrations across the particle populations, we were able to correctly identify a manufacturing process involving wet chemistry, rather than a dry mixing of two powders to give an overall chemical average. In conclusion, this demonstrates the utility of LIBS as a large-scale single particle analysis tool for nuclear forensics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Current Needs in Radiochemistry

There are a number of current needs in the development of the Pu and Am separations that underpin larger interest areas including nuclear waste issues, nuclear weapons, nuclear forensics, nuclear fuels and similarly related fields. In the large areas of interest, there are a number of sub-fields that include corrosion chemistry, pyrochemistry, solution-phase chemistry, rapid separations, environmental speciation, and other similar efforts. However, in all of the these fields it is important to realize that the underlying chemistry that underpins these efforts is similar in that Pu and Am are bound to ligands that can be in the solid, aqueous, or gas phase and separations occurs due to the preferential binding of the ligand to Pu or Am based on a number of factors that include pH, concentration, oxidation state, etc. In the past, most of the Pu and Am chemistry has occurred in limited scope within universities where micro-scale and bench-top scale chemistry are the dominate investigative theme. At US national laboratory and their international counterparts, larger scale reactions have been attempted such that industrial scale chemistry has been completed. Some of this technology has been harnessed in radiopharmaceuticals and nuclear fuel reprocessing. However, such bench-top research is expensive to due to the safety and security that is concerned when dealing with Pu, and scale-up of reactions is even more resource intensive. In an effort to offset this expensive, it would be of interest to explore the ability to predict selectivity based on the computational modeling of actinide chemistry. This has historically been limited by the abilities of large supercomputers, but with the emphasis on developing exascale computers within the US and similar efforts by other countries this predictive modeling has potential to produce significant results that would yield improved understanding of actinide chemistry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Evaluation of Properties for Microsample Identification

A study was conducted to determine if individual particle characteristics could be used to identify particles of interest, sub-samples, from bulk post-detonation debris. Three archived post-detonation debris samples were used for this effort. Particles from these samples were identified as active (produced fission tracks), and inactive (did not produce fission tracks), as the first defining characteristic. Morphology was the secondary characteristic to select particles for further study, i.e. spherical/non-spherical. Once particles were identified and isolated, they were characterized by optical microscopy for size in µm, number of fission tracks, morphology, transmitted light color, and reflected light color. Particles were then analyzed by scanning electron microscopy for morphology, elemental content, and compound identification. Raman spectroscopy was attempted on five particles with indeterminate results due to environmental mixing (heterogeneity) during the events of particle formation. Once all non-destructive analyses were completed all particles were analyzed by thermal ionization mass spectrometry to determine isotopic atom percents of plutonium and uranium, and an estimate of atoms of plutonium and uranium in each particle. An estimate of the ratio of uranium to plutonium was also obtained (U/Pu). Data analytics of the data from the particles showed that combining characteristics of the particles have a high probability of identifying particles of interest from bulk post-detonation debris samples. Please note that this version of the report is an abridged version of the full report (Wagnon et al. 2025) that has been edited to be appropriate for public release.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗