Oxygen Isotope and Fluorine Impurity Signatures during the Conversion of Uranium Ore Concentrates to Nuclear Fuel.

Within the front end of the nuclear fuel cycle, many processes impart forensic signatures. Oxygen-stable isotopes (δ18O values) of uranium-bearing materials have been theorized to provide the processing and geolocational signatures of interdicted materials. However, this signature has been minimally utilized due to a limited understanding of how oxygen isotopes are influenced during uranium processing. This study explores oxygen isotope exchange and fractionation between magnesium diuranate (MDU), ammonium diuranate (ADU), and uranyl fluoride (UO2F2) with steam (water vapor) during their reduction to UOx. The MDU was precipitated from two water sources, one enriched and one depleted in 18O. The UO2F2 was precipitated from a single water source and either directly reduced or converted to ADU prior to reduction. All MDU, ADU, and UO2F2 were reduced to UOx in a 10% hydrogen/90% nitrogen atmosphere that was dry or included steam. Powder X-ray diffraction (p-XRD) was used to verify the composition of materials after reduction as mixtures of primarily U3O8, U4O9, and UO2 with trace magnesium and fluorine phases in UOx from MDU and UO2F2, respectively. The bulk oxygen isotope composition of UOx from MDU was analyzed using fluorination to remove the lattice-bound oxygen, and then O2 was subsequently analyzed with isotope ratio mass spectrometry (IRMS). The oxygen isotope compositions of the ADU, UO2F2, and the resulting UOx were analyzed by large geometry secondary ion mass spectrometry (LG-SIMS). When reduced with steam, the MDU, ADU, and UO2F2 experienced significant oxygen isotope exchange, and the resulting δ18O values of UOx approached the values of the steam. When reduced without steam, the δ18O values of converted ADU, U3O8, and UOx products remained similar to those of the UO2F2 starting material. LG-SIMS isotope mapping of F impurity abundances and distributions showed that direct steam-assisted reduction from UO2F2 significantly removed F impurities while dry reduction from UO2F2 led to the formation of UOx that was enhanced in F impurities. In addition, when UO2F2 was processed via precipitation to ADU and calcination to U3O8, F impurities were largely removed, and reductions to UOx with and without steam each had low F impurities. Overall, these findings show promise for combining multiple signatures to predict the process history during the conversion of uranium ore concentrates to nuclear fuel.

Anthropogenic uranium signatures in turtles, tortoises, and sea turtles from nuclear sites.

Chelonians (turtles, tortoises, and sea turtles) grow scute keratin in sequential layers over time. Once formed, scute keratin acts as an inert reservoir of environmental information. For chelonians inhabiting areas with legacy or modern nuclear activities, their scute has the potential to act as a time-stamped record of radionuclide contamination in the environment. Here, we measure bulk (i.e. homogenized scute) and sequential samples of chelonian scute from the Republic of the Marshall Islands and throughout the United States of America, including at the Barry M. Goldwater Air Force Range, southwestern Utah, the Savannah River Site, and the Oak Ridge Reservation. We identify legacy uranium (235U and 236U) contamination in bulk and sequential chelonian scute that matches known nuclear histories at these locations during the 20th century. Our results confirm that chelonians bioaccumulate uranium radionuclides and do so sequentially over time. This technique provides both a time series approach for reconstructing nuclear histories from significant past and present contexts throughout the world and the ability to use chelonians for long-term environmental monitoring programs (e.g. sea turtles at Enewetok and Bikini Atolls in the Republic of the Marshall Islands and in Japan near the Fukushima Daiichi reactors).

Production of mixed element actinide reference particulates to support nuclear safeguards using THESEUS, an aerosol-based particulate synthetic methodology.

The THermally Evaporated Spray for Engineered Uniform particulateS (THESEUS) production platform was developed to generate highly uniform mixed actinide oxide particles. The particulate synthesis platform builds on previous efforts and utilizes an aerosol-based technology to generate, calcine, characterize, and aggregate a monodisperse oxide phase particle product. In this study, particles comprised of uranium oxide, incorporated with varying compositions of thorium, were produced. Th/U test materials with 232Th concentrations between 1 ppm and 10%, ratioed to 238U, were successfully generated with in situ calcination at 600 °C and characterized by in situ aerodynamic particle size spectrometry and ex situ microanalytical methods. Populations of monodisperse particulates (geometric standard deviation - GSD < 1.15) with an average diameter near 1 µm were generatated and micro-Raman spectroscopy of individual particles identified U3O8 as the primary material phase for the range of Th/U samples analyzed. Single particle measurements and automated particle analyses by secondary ion mass spectrometry (SIMS) were performed. Uniform inter-particle elemental and isotopic homogeneity for uranium and thorium isotopes was characterized by SIMS, and a 232Th/238U relative sensitivity factor of 0.53 was determined. SIMS results demonstrated differences in the 232Th/238U profiling behavior for Th/U particulates with increased Th content (>1%). Despite the observed profiling behavior, single particle measurements of the 10% Th sample indicate inter-particle homogeneity. This work represents the first systematic study of Th/U microparticulate reference materials generated and intended for nuclear safeguards applications and serves as a demonstration of THESEUS to support a sustained capability for the production mixed-element particulate reference materials.

Scarlet macaw (Ara macao) breeding at the Mimbres archaeological site of Old Town (early AD 1100s) in Southwestern New Mexico.

Examination of avian eggshell at the Old Town archaeological site in Southwestern New Mexico, United States of America, indicates that scarlet macaw (Ara macao) breeding occurred during the Classic Mimbres period (early AD 1100s). Current archaeological and archaeogenomic evidence from throughout the American Southwest/Mexican Northwest (SW/NW) suggests that Indigenous people bred scarlet macaws at an unknown location(s) between AD 900 and 1200 and likely again at the northwestern Mexico site of Paquimé post-AD 1275. However, there is a lack of direct evidence for breeding, or the location(s) of scarlet macaw breeding itself, within this area. This research, for the first time, provides evidence of scarlet macaw breeding using scanning electron microscopy of eggshells from Old Town.

Fully convolutional neural network for removing background in noisy images of uranium bearing particles.

A fully convolutional neural network (FCN) was developed to supersede automatic or manual thresholding algorithms used for tabulating SIMS particle search data. The FCN was designed to perform a binary classification of pixels in each image belonging to a particle or not, thereby effectively removing background signal without manually or automatically determining an intensity threshold. Using 8000 images from 28 different particle screening analyses, the FCN was trained to accurately predict pixels belonging to a particle with near 99% accuracy. Background eliminated images were then segmented using a watershed technique in order to determine isotopic ratios of identified particles. A comparison of the isotopic distributions of an independent data set segmented using the neural network with a commercially available automated particle measurement (APM) program developed by CAMECA was performed. This comparison highlighted the necessity for effective background removal to ensure that resulting particle identification is not only accurate, but preserves valuable signal that could be lost due to improper segmentation. The FCN approach improves the robustness of current state-of-the-art particle searching algorithms by reducing user input biases, resulting in an improved absolute signal per particle and decreased uncertainty of the determined isotope ratios.

Comparison of high-resolution and dynamic reaction cell ICP-MS capabilities for forensic analysis of iron in glass.

Forensic laboratories routinely conduct analysis of glass fragments to determine whether or not there is an association between a fragment(s) recovered from a crime scene or from a suspect to a particular source of origin. The physical and optical (refractive index) properties of the fragments are compared and, if a "match" between two or more fragments is found, further elemental analysis can be performed to enhance the strength of the association. A range of spectroscopic techniques has been used for elemental analysis of this kind of evidence, including inductively coupled plasma mass spectrometry (ICP-MS). Because of its excellent sensitivity, precision, and accuracy, several studies have found that ICP-MS methods (dissolution and laser-ablation) provide the best discrimination between glass fragments originating from different sources. Nevertheless, standard unit-resolution ICP-MS instruments suffer from polyatomic interferences including (40)Ar(16)O(+), (40)Ar(16)O(1)H(+), and refractory oxide (40)Ca(16)O(+) that compromise measurements of trace levels of Fe(56+) and Fe(57+), for example. This is a drawback in the analysis of glass fragments because iron has been previously identified as a good discriminating element. Currently, several techniques are available that enable reduction of such interferences. However, there are no data comparing detection limits of iron in glass using those techniques. The aim of this study was to compare, the analytical performance of high-resolution sector field inductively coupled plasma mass spectrometry (HR-SF-ICP-MS) and quadrupole ICP-MS equipped with a dynamic reaction cell (DRC-ICP-MS), for the detection of iron in glass, in terms of accuracy, precision, and method detection limits (MDLs). Analyses were conducted using conventional acid-digestion and laser-ablation methods. For laser-ablation analyses, carrier gases were compared to assess the effect on detection limits in the detection of iron isotopes. Iron polyatomic interferences were reduced or resolved by using a dynamic reaction cell and high-resolution ICP-MS. MDLs as low as 0.03 microg g(-1) and 0.14 microg g(-1) were achieved in laser-ablation and solution-based analyses, respectively. Use of helium as carrier gas improved detection limits for both iron isotopes in medium-resolution HR-SF-ICP-MS and in DRC-ICP-MS.