William S. Kinman

Neptunium incorporation in sodium-substituted metaschoepite

Abstract Uranyl oxide hydrate minerals are common in the altered zones of U deposits and are expected to form where spent nuclear fuel is altered in an oxidizing environment. Consistent with all known uranyl oxide hydrate minerals, metaschoepite [(UO2)4O(OH)6](H2O)5, contains sheets of uranyl polyhedra with H2O groups located in the interlayer. Several crystals along the series from metaschoepite to Na-substituted metaschoepite (Na-MS), approximate formula Na[(UO2)4O2(OH)5](H2O)5, have been synthesized and their structures have been determined. Each contains sheets of uranyl pentagonal bipyramids that are topologically identical to those in metaschoepite, schoepite and fourmarierite. The sheets are electroneutral in metaschoepite, but substitution of O for OH located at the equatorial vertices of the uranyl polyhedra gives a charged sheet that is balanced by incorporation of Na in the interlayer. Synthesis of crystals of Na-MS from a solution containing ~500 ppm Np5+, followed by analysis of the crystals using laser-ablation inductively coupled-plasma mass-spectroscopy, demonstrated that the crystals incorporate Np. This is in contrast to earlier studies that showed no incorporation of Np5+ in synthetic metaschoepite (which has electroneutral sheets), and supports the hypothesis that Np5+ incorporation is more likely in uranyl oxide hydrates with charged species in the interlayer.

Validation of reference materials for uranium radiochronometry in the frame of nuclear forensic investigations

The results of a joint effort by expert nuclear forensic laboratories in the area of age dating of uranium, i.e. the elapsed time since the last chemical purification of the material are presented and discussed. Completely separated uranium materials of known production date were distributed among the laboratories, and the samples were dated according to routine laboratory procedures by the measurement of the (230)Th/(234)U ratio. The measurement results were in good agreement with the known production date showing that the concept for preparing uranium age dating reference material based on complete separation is valid. Detailed knowledge of the laboratory procedures used for uranium age dating allows the identification of possible improvements in the current protocols and the development of improved practice in the future. The availability of age dating reference materials as well as the evolvement of the age dating best-practice protocol will increase the relevance and applicability of age dating as part of the tool-kit available for nuclear forensic investigations.

Round-robin 230Th–234U age dating of bulk uranium for nuclear forensics

In an inter-laboratory measurement comparison study, four laboratories determined 230Th–234U model ages of uranium certified reference material NBL U050 using isotope dilution mass spectrometry. The model dates determined by the participating laboratories range from 9 March 1956 to 19 October 1957, and are indistinguishable given the associated measurement uncertainties. These model ages are concordant with to slightly older than the known production age of NBL U050.

Polyatomic interferences on high precision uranium isotope ratio measurements by MC-ICP-MS: Applications to environmental sampling for nuclear safeguards

Modern mass spectrometry and separation techniques have made measurement of major uranium isotope ratios a routine task; however accurate and precise measurement of the minor uranium isotopes remains a challenge as sample size decreases. One particular challenge is the presence of isobaric interferences and their impact on the accuracy of minor isotope 234U and 236U measurements. We present techniques used for routine U isotopic analysis of environmental nuclear safeguards samples and evaluate polyatomic interferences that negatively impact accuracy as well as methods to mitigate their impacts.

Measurements of extinct fission products in nuclear bomb debris: Determination of the yield of the Trinity nuclear test 70 y later

Significance This work describes an approach to postdetonation nuclear forensics involving isotopic measurements that allows for characterization of a nuclear detonation at any time. By performing high-precision measurements of stable isotope perturbations in nuclear bomb debris, it is possible to quantify short-lived fission products long after they have decayed below radiometric detection limits and become extinct. The extinct fission product concentrations can be used to reconstruct details of the nuclear device months to years after the detonation occurred. The approach is demonstrated by analysis of debris from the Trinity nuclear test and new estimates of the efficiency and yield of the historic test are presented. This paper describes an approach to measuring extinct fission products that would allow for the characterization of a nuclear test at any time. The isotopic composition of molybdenum in five samples of glassy debris from the 1945 Trinity nuclear test has been measured. Nonnatural molybdenum isotopic compositions were observed, reflecting an input from the decay of the short-lived fission products 95Zr and 97Zr. By measuring both the perturbation of the 95Mo/96Mo and 97Mo/96Mo isotopic ratios and the total amount of molybdenum in the Trinity nuclear debris samples, it is possible to calculate the original concentrations of the 95Zr and 97Zr isotopes formed in the nuclear detonation. Together with a determination of the amount of plutonium in the debris, these measurements of extinct fission products allow for new estimates of the efficiency and yield of the historic Trinity test.

A geochemical approach to constraining the formation of glassy fallout debris from nuclear tests

Glassy nuclear fallout debris from near-surface nuclear tests is fundamentally reprocessed earth material. A geochemical approach to analysis of glassy fallout is uniquely suited to determine the means of reprocessing and shed light on the mechanisms of fallout formation. An improved understanding of fallout formation is of interest both for its potential to guide post-detonation nuclear forensic investigations and in the context of possible affinities between glassy debris and other glasses generated by high-energy natural events, such as meteorite impacts and lightning strikes. This study presents a large major-element compositional dataset for glasses within aerodynamic fallout from the Trinity nuclear test (“trinitite”) and a geochemically based analysis of the glass compositional trends. Silica-rich and alkali-rich trinitite glasses show compositions and textures consistent with formation through melting of individual mineral grains—quartz and alkali feldspar, respectively—from the test-site sediment. The volumetrically dominant glass phase—called the CaMgFe glass—shows extreme major-element compositional variability. Compositional trends in the CaMgFe glass are most consistent with formation through volatility-controlled condensation from compositionally heterogeneous plasma. Radioactivity occurs only in CaMgFe glass, indicating that co-condensation of evaporated bulk ground material and trace device material was the main mechanism of radioisotope incorporation into trinitite. CaMgFe trinitite glasses overlap compositionally with basalts, rhyolites, fulgurites, tektites, and microtektites but display greater compositional diversity than all of these naturally formed glasses. Indeed, the most refractory CaMgFe glasses compositionally resemble early solar system condensates—specifically, CAIs.

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.

US-DOE and CIAE international cooperation in age-dating uranium standards

In 2014 the United States Department of Energy and the China Institute of Atomic Energy collaborated in a study measuring the model ages of uranium certified reference materials. Lawrence Livermore National Laboratory (LLNL) and Los Alamos National Laboratory (LANL), and the Chinese Institute of Atomic Energy (CIAE) determined 230Th–234U model ages for uranium certified reference materials U010 and U850. The aim of this work was to collaborate with CIAE and compare methods for measuring the age of bulk uranium materials using the 230Th–234U radiochronometer. Accurate results for age-dating depend on the accurate calibration of the tracer materials (e.g., 229Th and 233U) used for the isotope dilution mass spectrometry (IDMS) analyses. To facilitate inter-comparison of results, samples of a 230Th standard reference material were distributed to each laboratory for 229Th tracer inter-calibration. The resulting 230Th–234U model ages from this collaboration for U010 ranged from March 1956 to January 1959, which agree with the known material production date of June 5th, 1958. The determined model ages for U850 were from December 1955 to October 1957, which agree with the material production date of December 31, 1957. All three laboratories used independent methods to determine model ages for uranium standards that agree with known production ages and with previously reported results.

New determination of the 229Th half-life

A new determination of the 229Th half-life was made based on measurements of the 229Th massic activity of a high-purity solution for which the 229Th molality had previously been measured. The 229Th massic activity was measured by direct comparison with SRM 4328C using 4παβ liquid scintillation counting, NaI counting, and standard addition liquid scintillation counting. The massic activity was confirmed by isotope dilution alpha spectrometry measurements. The calculated 229Th half-life is (7825 ± 87) years (k = 2), which is shorter than the three most recent half-life determinations but is consistent with these values within uncertainties.

Determination of Volatility and Element Fractionation in Glassy Fallout Debris by SIMS

The purpose of this report is to characterize glassy fallout debris using the Trinity Test and then characterize the U-isotopes of U3O8 reference materials that contain weaponized debris.