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At least 1,495 records · Page 83

Tn-seq of Caulobacter crescentus under uranium stress reveals genes essential for detoxification and stress tolerance

Ubiquitous aquatic bacterium Caulobacter crescentus is highly resistant to uranium (U) and facilitates U biomineralization and thus holds promise as an agent of U bioremediation. In order to gain an understanding of how C. crescentus tolerates U, we employed transposon (Tn) mutagenesis paired with deep sequencing (Tn-seq) in a global screen for genomic elements required for U resistance. Of the 3,879 annotated genes in the C. crescentus genome, 37 were found to be specifically associated with fitness under U stress, 15 of which were subsequently tested through mutational analysis. Systematic deletion analysis revealed that mutants lacking outer membrane transporters (rsaFa and rsaFb), a stress-responsive transcription factor (cztR), or a ppGpp synthetase/hydrolase (spoT) exhibited a significantly lower survival rate under U stress. RsaFa and RsaFb, which are homologues of TolC in Escherichia coli, have previously been shown to mediate S-layer export. Transcriptional analysis revealed upregulation of rsaF a and rsaF b by 4- and 10-fold, respectively, in the presence of U. We additionally show that rsaFa mutants accumulated higher levels of U than the wild type, with no significant increase in oxidative stress levels. These results suggest a function for RsaF a and RsaF b in U efflux and/or maintenance of membrane integrity during U stress. In addition, we present data implicating CztR and SpoT in resistance to U stress. Together, our findings reveal novel gene targets that are key to understanding the molecular mechanisms of U resistance in C. crescentus.

59 BASIC BIOLOGICAL SCIENCES↗

Electrochemical Nucleation and Growth of Uranium and Plutonium from Molten Salts

This work examines the nucleation and growth behavior of uranium and plutonium from molten LiCl-KCl eutectic on inert electrodes using electrochemical techniques. Current-time transients obtained from chronoamperometric experiments were compared with theoretical models to characterize the type of nucleation (progressive or instantaneous) for deposition of U and Pu, and co-deposition of U-Pu, from molten LiCl-KCl at inert electrodes. It was established that the nucleation mode of actinides present as chlorides in molten chloride salts changes from progressive to instantaneous with an increasing concentration of the trivalent actinide ions in the salt. The effect of the material of the working electrode was investigated, and it was found that changing the material from tungsten to silver improves resolvability of the nucleation peaks and allows more accurate analysis of the experimental measurements. Using the nucleation data, diffusion coefficients were obtained for U 3+ and Pu 3+ , and were found to be in very good agreement with the values obtained from other studies. Furthermore, the density of nuclei produced during instantaneous nucleation, the rate of nucleation for progressive nucleation, and the radius of the deposited nuclei were evaluated and examined at different overpotentials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Laser-Induced Breakdown Spectroscopy (LIBS) Measurement of Uranium in Molten Salt

In this current study, the molten salt aerosol–laser-induced breakdown spectroscopy (LIBS) system was used to measure the uranium (U) content in a ternary UCl 3 –LiCl–KCl salt to investigate and assess a near real-time analytical approach for material safeguards and accountability. Experiments were conducted using five different U concentrations to determine the analytical figures of merit for the system with respect to U. In the analysis, three U lines were used to develop univariate calibration curves at the 367.01 nm, 385.96 nm, and 387.10 nm lines. The 367.01 nm line had the lowest limit of detection (LOD) of 0.065 wt% U. The 385.96 nm line had the best root mean square error of cross-validation (RMSECV) of 0.20 wt% U. In addition to the univariate calibration approach, a multivariate partial least squares (PLS) model was developed to further analyze the data. Using partial least squares (PLS) modeling, an RMSECV of 0.085 wt% U was determined. The RMSECV from the multivariate approach was significantly better than the univariate case and the PLS model is recommended for future LIBS analysis. Overall, the aerosol-LIBS system performed well in monitoring the U concentration and it is expected that the system could be used to quantitatively determine the U compositions within the normal operational concentrations of U in pyroprocessing molten salts.

Williams, Ammon↗

Coupling of the Liquid Sampling–Atmospheric Pressure Glow Discharge to Orbitrap Mass Analyzers for Uranium Isotope Ratio Analysis: Evolution of the Methodology and Implications to the Field

Just over a decade ago, a truly outside-of-the-box approach to isotope ratio mass spectrometry (IRMS) was undertaken between research groups at Clemson University and the Pacific Northwest National Laboratory. The original motivation dealt with projections as to whether or not microplasmas could be developed into practical elemental ionization sources, perhaps for transportable analysis applications. In particular, the use of the liquid sampling–atmospheric pressure glow discharge (LS-APGD) was pursued. Its interfacing to an ultra-high resolution Orbitrap platform, proved not only facile, but opened up a wealth of potential applications. Here, we lay out a historical, tutorial description of the interfacing and the evolution of the methodology regarding IRMS of uranium. Practical challenges and opportunities are described, which hopefully provide guidance to further applications in high resolution IRMS. It is hoped that, while detailed and lengthy, the didactic nature of the presentation provides experimental insights and tips, and also serves as an homage to our very good friend, Professor Gary M. Hieftje, whose scientific inspiration and comradery have been immeasurably important in our own careers.

Koppenaal, David W.↗

Characterization of Blistering and Delamination in Depleted Uranium Hohlraums

Blistering and delamination are the primary failure mechanisms during the processing of depleted uranium (DU) hohlraums. These hohlraums consist of a sputter-deposited DU layer sandwiched between two sputter-deposited layers of gold; a final thick gold layer is electrodeposited on the exterior. The hohlraum is deposited on a copper-coated aluminum mandrel; the Al and Cu are removed with chemical etching after the gold and DU layers are deposited. After the mandrel is removed, blistering and delamination are observed on the interiors of some hohlraums, particularly at the radius region. It is hypothesized that blisters are caused by pinholes in the copper and gold layers; etchant leaking through these holes reaches the DU layer and causes it to oxidize, resulting in a blister. Depending on the residual stress in the deposited layers, blistering can initiate larger-scale delamination at layer interfaces. Scanning electron microscopy indicates that inhomogeneities in the machined aluminum mandrel are replicated in the sputter-deposited copper layer. Furthermore, the Cu layer exhibits columnar growth with pinholes that likely allow etchant to come in contact with the gold layer. Any inhomogeneities or pinholes in this initial gold layer then become nucleation sites for blistering. Using a focused ion beam system to etch through the gold layer and extract a cross-sectional sample for transmission electron microscopy, amorphous, intermixed layers at the gold/DU interfaces are observed. Nanometer-sized bubbles in the sputtered and electrodeposited gold layers are also present. Characterization of the morphology and composition of the deposited layers is the first step in determining modifications to processing parameters, with the goal of attaining a significant improvement in hohlraum yield.

36 MATERIALS SCIENCE↗

Technical basis for the use of a correlated neutron source in the uranium neutron coincidence collar

Active neutron coincidence systems are commonly used by international inspectorates to verify a material balance across the various stages of the nuclear fuel cycle. The Uranium Neutron Coincidence Collar (UNCL) is one such instrument; it is used to measure the linear density of 235 U (g 235 U/cm of active length in assembly) in fresh light water reactor fuel in nuclear fuel fabrication facilities. The UNCL and other active neutron interrogation detectors have historically relied on americium lithium ( 241 AmLi) sources to induce fission within the sample in question. Californium-252 is under consideration as a possible alternative to the traditional 241 AmLi source. Finally, this work relied upon a combination of experiments and Monte Carlo simulations to demonstrate the technical basis for the replacement of 241 AmLi sources with 252 Cf sources by evaluating the statistical uncertainty in the measurements incurred by each source and assessing the penetrability of neutrons from each source for the UNCL.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

U M subshell X-ray emission spectroscopy of uranium dioxide: the effect of excitation energy

There are very great differences between the non-resonant U M subshell X-ray Emission Spectra of Uranium Dioxide generated with low and high-energy excitation. Additionally, these different spectra are each supported by theoretical constructs. It will be shown that the differences between these experimental spectra can be reconciled and the utility of both theoretical approaches confirmed, including the use of FEFF in the low energy and high-energy regimes.

36 MATERIALS SCIENCE↗

Neutron Leakage Spectrum from a Pulsed Uranium Sphere [Slides]

The neutron leakage spectrum from a pulsed uranium sphere was calculated with MCNP5 and found to be in good agreement with previous “MCN” simulations and experimental data. This example is proposed as another time-of-flight (TOF) test problem for NUEXS, a code for diagnostic simulation maintained by LANL Group P-23.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Multispectral Gamma-Ray Analysis Using Clover Detectors with Application to Uranium Fission Product Analysis

A high-efficiency gamma-ray counting system has been built at Los Alamos National Laboratory for use in analyzing nuclear forensics samples. This system consists of two clover high-purity germanium detectors and is surrounded by a thallium-doped sodium iodide annulus. Special precautions have been taken to ensure the system has a low background. The system is connected to XIA Pixie-4 fast digitizers and collects data in list-mode. This work is split into two main parts. The first part describes the proper steps and techniques to initialize the settings of a detector system connected to fast digitizers in order to optimize the system for resolution and throughput. The various counting modes for this particular system are described in detail, including the benefits and drawbacks of each mode. Steps are then shown to characterize the system by obtaining efficiency curves for various counting modes and sample geometries. Because of the close counting geometry involved with this system, true coincidence summing factors must be calculated, and are done so in part by measuring the peak-to-total ratios of the system in its various counting modes across a wide energy range. The dead-time for the system can be complicated due to the multiple inputs of the system. Techniques for calculating the dead-time of multiple-detector systems are discussed. The second part of this work shows the system’s usefulness in analyzing nuclear forensics samples, specifically irradiated enriched uranium. Three fission product parent-daughter pairs of different lifetimes are analyzed over a course of six months. The activities of each nuclide are calculated at each time step. Age dating techniques using the parent-daughter pairs are discussed, as well as the detection limits of each nuclide for a range of sample ages. Finally, avenues for further research are presented, as well as potential sources of error or uncertainty for this work.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Determination of 99 Mo, 103 Ru, and 140 Ba Activity in an Irradiated Solution of Low Enriched Uranium Using Gamma Ray Spectroscopy

The need for technologies and methods to produce 99m Tc outside of the conventional nuclear reactor process has continued to grow over the past decade. Consequently, more work and research have been done to produce 99 Mo using less traditional methods. In this work, a 300.7 mL solution containing low enriched uranium was irradiated with a linear accelerator. A portion of the sample was then counted with a gamma ray spectrometer to determine the activities of 99 Mo, 103 Ru, and 140 Ba in the solution at the end of the irradiation. The activities at the end of the irradiation were determined to be 68.00 ± 3.84, 3.835 ± 0.226, and 20.47 ± 1.07 mCi, respectively, in the 300.7 mL solution.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Control of a Uranium-Hydride Reactor with Deuterium-Hydrogen Exchange

A 70 MWt reactor is evaluated that utilizes uranium-hydride fuel and is cooled by lead-bismuth eutectic (LBE). The concept utilizes a high-density, high-density-fuel outer annulus which surrounds a lowdensity, powder-fuel central core. Prior to reactor startup, the entire core is initially saturated with deuterium (UD3). To start the reactor, hydrogen flows through the central, low density powder (with protons gradually replacing deuterons) until criticality is reached. Over the remaining lifetime of the reactor, with the goal of 10 years, hydrogen is continually added to the outer, high-density core to compensate for burnup reactivity loss. Throughout lifetime, the inner region serves as a standard control/shutdown rod, with the ability to replace the H with D relatively quickly (because of the low density, high surface area of the fuel). The scope of this work is to determine if a reactor could be designed to meet the above guidelines and if possible estimate the size of the smallest reactor that could meet the guidelines.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Laboratory demonstration of a multi-sensor unattended cylinder verification station for uranium enrichment plant safeguards

The objective of safeguards is the timely detection of the diversion of a significant quantity of nuclear materials, and safeguarding uranium enrichment plants is especially important in preventing the spread of nuclear weapons. The IAEA’s proposed Unattended Cylinder Verification Station (UCVS) for UF 6 cylinder verification would combine the operator’s accountancy scale with a nondestructive assay system such as the Passive Neutron Enrichment Meter (PNEM) and cylinder identification and surveillance systems. In this project, we built a laboratory-scale UCVS and demonstrated its capabilities using mock UF 6 cylinders. We developed a signal processing algorithm to automate the data collection and processing from four continuous, unattended sensors. The laboratory demonstration of the system showed that the software could successfully identify cylinders, snip sensor data at the appropriate points in time, determine the relevant characteristics of the cylinder contents, check for consistency among sensors, and output the cylinder data to a file. This paper describes the equipment, algorithm and software development, laboratory demonstration, and recommendations for a full-scale UCVS.

42 ENGINEERING↗

Empirical and physics based mathematical models of uranium hydride decomposition kinetics with quantified uncertainties.

Metal particle beds have recently become a major technique for hydrogen storage. In order to extract hydrogen from such beds, it is crucial to understand the decomposition kinetics of the metal hydride. We are interested in obtaining a a better understanding of the uranium hydride (UH3) decomposition kinetics. We first developed an empirical model by fitting data compiled from different experimental studies in the literature and quantified the uncertainty resulting from the scattered data. We found that the decomposition time range predicted by the obtained kinetics was in a good agreement with published experimental results. Secondly, we developed a physics based mathematical model to simulate the rate of hydrogen diffusion in a hydride particle during the decomposition. We used this model to simulate the decomposition of the particles for temperatures ranging from 300K to 1000K while propagating parametric uncertainty and evaluated the kinetics from the results. We compared the kinetics parameters derived from the empirical and physics based models and found that the uncertainty in the kinetics predicted by the physics based model covers the scattered experimental data. Finally, we used the physics-based kinetics parameters to simulate the effects of boundary resistances and powder morphological changes during decomposition in a continuum level model. We found that the species change within the bed occurring during the decomposition accelerates the hydrogen flow by increasing the bed permeability, while the pressure buildup and the thermal barrier forming at the wall significantly impede the hydrogen extraction.

08 HYDROGEN↗

Rapid, autonomous analysis of HPGe gamma-ray spectra II: Uranium identification and characterization

RadID is a gamma-ray spectrum analysis program originally written to assist in the detection of the illicit movement of nuclear material. In this second of the three-document series we discuss how RadID detects the presence of uranium isotopes and determines a number of its characteristics, most notably or processed material and enriched estimates.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗