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At least 325 records · Page 18

K 2 CO 3 /18-Crown-6-Catalyzed Selective H/D Exchange of Heteroarenes with Bromide as a Removable Directing Group

Here, the K 2 CO 3 /18-crown-6-catalyzed H/D exchange of heretoarenes in high atom % deuterium incorporation is disclosed. The use of a weak base as a catalyst leads to excellent site selectivity and broad functional group tolerance. Control experiments indicated that the use of bromide, which enhances the adjacent C–H bond reactivity, as a removable directing group is essential. Moreover, conversion of bromide to other functional groups is also performed to construct other useful deuterated compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Radial Chemistry of Getter Components in Light Water Reactors via Controlled Electrochemical Dissolution

Getters are among the key functional components in the Tritium Producing Burnable Absorber Rods (TPBARs) of Light Water Reactors, and are used to capture the released tritium gas. They are cylindrical tubes comprised of the alloy zircaloy-4 which is coated with nickel plating both internally and externally. Their exposure to tritium as well as the irradiation environments in the light water reactors changes their structure, chemical composition and chemistry. Understanding the radial tritium distribution is key to gaining insight into the evolution of new chemistry upon irradiation in order to predict getter performance. Consequently, efforts are underway to devise a method that can allow selective probing into the getter core radially to probe the chemistry akin to carefully and selectively peeling of the layers of an onion. We have recently devised an electrochemical dissolution technique for controlled radial dissolution of zirconium based liners; this work describes the first proof-of-concept demonstration of the applicability of this technique on the controlled radial dissolution of nickel plated getters. The technique is complemented with periodic analysis of the electrolyte solution to measure the rates of release of the various elemental components and therefore glean information on their radial distribution across the getter; further complementary microscopy on the exposed surfaces allows us insight into the chemistry at the getter core.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Multicomponent mutual diffusion in the warm, dense matter regime

We present a study in the warm, dense matter regime of transport properties for a ternary mixture of the isotopes of hydrogen at 5 g/cm3 at temperatures between 50 and 400 eV as well as for a quaternary system with added carbon at 20 g/cm3 and 10 eV. We determine the properties from a series of orbital-free molecular dynamics simulations and calculate the diffusion coefficients in the Maxwell–Stefan (MS) formulation. The Darken approximation, which includes only time correlations between the same atom of the same species, gives reasonable agreement with the full MS results. However, we find that the reasons for this concurrence rest with more complex, and somewhat subtle, details within the MS prescription.

Ticknor, C. (ORCID:0000000199724524)↗

Effect of a Cr-rich surface layer on D retention in various RAFM steels

In this work, deuterium (D) retention is compared between various reduced-activation ferritic/martensitic steels, including CLF-1, Eurofer, F82H, and Rusfer, exposed to pure D plasma (ion flux ~1.5–2 × 10 21 m -2 s -1 , fluence, ϕ D , ~1 × 10 25 m -2 , sample temperature ~373 K, and incident ion energy ~100 eV). It is found that there is a large difference (up to ~30x) in the D retention between CLF-1 and F82H even with the same plasma exposure condition and similar nominal composition. The ϕ D dependence of the D retention exhibits a peculiar, counterintuitive feature: the D retention decreases with an increase in ϕ D from 2 × 10 23 m -2 to 1 × 10 25 m -2 . Surface analyses reveal that a Cr-rich surface layer is formed during outgassing at 773 K for 1 h before plasma exposure, and that there exists a clear correlation between the D retention and the Cr content in the surface layer.

36 MATERIALS SCIENCE↗

Tritiated Water Disposition Strategies

Tritium, a radioactive isotope of hydrogen, is typically confined within one or more confinement barriers. Tritium readily reacts with oxygen to form tritiated water or can exchange with protium or deuterium atoms in water to create tritiated water which is around 10,000 times more toxic than elemental tritium. Primary tritium confinement systems can create small volumes of highly tritiated water. Secondary confinement systems, like inert gloveboxes, will produce larger volumes of lower concentration tritiated water. Much larger volumes of tritiated water of very low tritium content are produced by tritium permeation/diffusion. Tritium from inside primary and secondary confinement barriers will diffuse from these systems into cooling water systems. Closed loop, recirculating cooling water systems will slowly accumulate tritium and create concentrations which exceed drinking water (or permitted discharge) concentrations. The cooling water systems designed as series of interconnected cooling loops that can slowly transfer tritium from one cooling loop to another cooling loop through heat exchangers. These large volumes of tritiated water may be above federal discharge limits and also lack convenient disposition pathways. This document will discuss tritiated water management strategies from the perspective of large volume, low tritium concentrations that exceed drinking water or permitted discharge limits. Applicable US regulatory requirements for a Molybdenum-99 (Mo-99) production facility concerning tritiated water are also cited. Tritiated water disposition options, based on typical waste minimization strategies will guide dispositions options. A Case Study example is presented to illustrate the pros and cons of several disposition options. The report does not recommend any particular disposition pathway but discusses strategies to be explored by a producer to guide selection of processes which best fits the needs of a particular waste stream.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Tritium Fires: Simulation and Safety Assessment

This is the Sandia report from a joint NSRD project between Sandia National Labs and Savannah River National Labs. The project involved development of simulation tools and data intended to be useful for tritium operations safety assessment. Tritium is a synthetic isotope of hydrogen that has a limited lifetime, and it is found at many tritium facilities in the form of elemental gas (T 2 ). The most serious risk of reasonable probability in an accident scenario is when the tritium is released and reacts with oxygen to form a water molecule, which is subsequently absorbed into the human body. This tritium oxide is more readily absorbed by the body and therefore represents a limiting factor for safety analysis. The abnormal condition of a fire may result in conversion of the safer T 2 inventory to the more hazardous oxidized form. It is this risk that tends to govern the safety protocols. Tritium fire datasets do not exist, so prescriptive safety guidance is largely conservative and reliant on means other than testing to formulate guidelines. This can have a consequence in terms of expensive and/or unnecessary mitigation design, handling protocols, and operational activities. This issue can be addressed through added studies on the behavior of tritium under representative conditions. Due to the hazards associated with the tests, this is being approached mainly from a modeling and simulation standpoint and surrogate testing. This study largely establishes the capability to generate simulation predictions with sufficiently credible characteristics to be accepted for safety guidelines as a surrogate for actual data through a variety of testing and modeling activities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Psychrometric Analysis for New NuMI Evaporator Weather Station

Tritium (H-3) is a weakly radioactive isotope of hydrogen and is a byproduct of accelerator operations at Fermi National Accelerator Laboratory (Fermilab). The Neutrinos at the Main Injector (NuMI) target produced tritiated condensate exhausted via the MI-65 building evaporators. Re-condensation of tritium evaporate was observed on the MI-65 rooftop, on nearby buildings, and on the surrounding grounds due to inefficiency of the existing evaporator system. A new evaporator system is being designed to eliminate re-condensation, and psychrometric data (temperature, humidity and dew point) plays a vital role in determining the location of a weather station to control the new evaporator system.

Alvarado-Anderson, Chase↗

Tritium Safety: Self-Study Course 11952

Course Overview: Tritium is a radioactive isotope of hydrogen which has characteristics that require workers understand what should be done to work safely and responsibly around it. Tritium is used for defense applications, experimental purposes for general research, and is a byproduct of some of the work that is done at LANL. Practical guidance offered in this training will inform safe handling to minimize negative impacts on personnel, the workspace, and the surrounding environment. This course, Tritium Safety Self-Study (Course 11952), provides information on the physical, chemical, and radioactive properties of tritium; sources of tritium; uses of tritium; biological effects of tritium; radiological control methods for tritium; monitoring methods of tritium; tritium waste minimization and handling; and alarms and proper response to abnormal conditions in a tritium facility. Course Objectives: When you have completed this course, you will be able to: Identify the physical, chemical, and radioactive properties of tritium; Identify the sources of tritium; Identify the uses of tritium; Identify the modes of tritium exposure; Identify the biological effects of tritium; Identify the radiological control methods of tritium; Identify methods used to monitor for tritium; Identify tritium waste minimization and handling techniques; Identify proper response to abnormal conditions in tritium facilities.

61 RADIATION PROTECTION AND DOSIMETRY↗

Small-Angle Neutron Scattering for Studying Lipid Bilayer Membranes

Small-angle neutron scattering (SANS) is a powerful tool for studying biological membranes and model lipid bilayer membranes. The length scales probed by SANS, being from 1 nm to over 100 nm, are well-matched to the relevant length scales of the bilayer, particularly when it is in the form of a vesicle. However, it is the ability of SANS to differentiate between isotopes of hydrogen as well as the availability of deuterium labeled lipids that truly enable SANS to reveal details of membranes that are not accessible with the use of other techniques, such as small-angle X-ray scattering. In this work, an overview of the use of SANS for studying unilamellar lipid bilayer vesicles is presented. The technique is briefly presented, and the power of selective deuteration and contrast variation methods is discussed. Approaches to modeling SANS data from unilamellar lipid bilayer vesicles are presented. Finally, recent examples are discussed. While the emphasis is on studies of unilamellar vesicles, examples of the use of SANS to study intact cells are also presented.

59 BASIC BIOLOGICAL SCIENCES↗

Nuclear composition of solar cosmic rays

Experimental observations of the elemental and isotopic composition of solar flare particles are discussed. Sources and characteristics of particle-emitting solar flare events are reviewed, and techniques for separating particle species are briefly described. Data are presented for the elemental composition of the solar atmosphere, and the possibility of determining the solar helium abundance from solar cosmic-ray observations is explored. The main experimental determinations of heavy element abundances at energies greater and less than 10 MeV/nucleon are summarized, and techniques for measuring the ionic charge composition of solar cosmic rays are outlined. Models explaining heavy element enhancements are described along with processes leading to gamma-ray emission during solar flare events. Observations of the rare isotopes of hydrogen and helium during solar flare events are noted, and a lower atmospheric limit is derived for nuclear reactions leading to positron decay. The possibility of investigating low-energy solar cosmic rays by measuring the relative abundances of different elements is evaluated.

Hovestadt, D.↗

Variational calculations of muonic-molecule energy levels

The best variational energies obtained to date of the bound states of muonic molecules containing nucleons of unit charge or isotopes of hydrogen are reported. Hylleraas wave functions are used to describe the three-particle systems, and the convergence of the energies is carefully studied; as many as 440 terms have been included in some cases. These results are compared with the best previous values.

Bhatia, A. K.↗

Reduction and analysis of data from experiment CAI on the IMP-8 mission

The Caltech Electron/Isotope Spectrometer (EIS) on the Interplanetary Monitoring Platform 8 (IMP-8) has provided precise measurements of the energy spectra and time variations of low energy electrons (0.16 to 6 MeV), the isotopes of hydrogen and helium (approximately 2 to 40 MeV/nucleon), and the elements from lithium through oxygen (approximately 5 to 50 MeV/nucleon) in energetic particle fluxes of solar, galactic, interplanetary, and magnetospheric origin since 1973. The accomplishments that have resulted from EIS measurements during the period March 24, 1980 to December 31, 1984 are summarized.

Stone, E. C.↗

Venusian hydrology: Steady state reconsidered

In 1987, Grinspoon proposed that the data on hydrogen abundance, isotopic composition, and escape rate were consistent with the hypothesis that water on Venus might be in steady state rather than monotonic decline since the dawn of time. This conclusion was partially based on a derived water lifetime against nonthermal escape of approximately 10(exp 8) yr. De Bergh et al., preferring the earlier Pioneer Venus value of 200 ppm water to the significantly lower value detected by Bezard et al., found H2O lifetimes of greater than 10(exp 9) yr. Donahue and Hodges derived H2O lifetimes of 0.4-5 x 10 (exp 9) yr. Both these analyses used estimates of H escape flux between 0.4 x 10(exp 7) and 1 x 10(exp 7) cm(exp -2)s(exp -1) from Rodriguez et al. Yet in more recent Monte Carlo modeling, Hodges and Tinsley found an escape flux due to charge exchange with hot H(+) of 2.8 x 10(exp 7) cm(exp -2)s(exp -1). McElroy et al. estimated an escape flux of 8 x 10(exp 6) cm(exp -2)s(exp -1) from collisions with hot O produced by dissociative recombination of O2(+). Brace et al. estimated an escape flux of 5 x 10(exp 6) cm(exp -2)s(exp -1) from ion escape from the ionotail of Venus. The combined estimated escape flux from all these processes is approximately 4 x 10(exp 7) cm(exp -2)s(exp -1). The most sophisticated analysis to date of near-IR radiation from Venus' nightside reveals a water mixing ratio of approximately 30 ppm, suggesting a lifetime against escape for water of less than 10(exp 8) yr. Large uncertainties remain in these quantities, yet the data point toward a steady state. Further evaluation of these uncertainties, and new evolutionary modeling incorporating estimates of the outgassing rate from post-Magellan estimates of the volcanic resurfacing rate are presented.

Grinspoon, David H.↗

Evolutionary implications of a steady-state water abundance on Venus

In 1987, Grinspoon proposed that the data on hydrogen abundance, isotopic composition, and escape rate were consistent with the hypothesis that water on Venus might be in steady-state rather than monotonic decline since the dawn of time. This conclusion was partially based on a derived water lifetime against nonthermal escape of approximately 10(exp 8) years. Others have questioned this conclusion. De Bergh et al. found H2O lifetimes of greater than 10(exp 9) years. Donahue and Hodges derived H2O lifetimes of 0.4 - 5 x 10(exp 9) years. The most sophisticated analysis to date of near-IR radiation from Venus' nightside reveals a water mixing ratio of approximately 30 ppm. Recent re-analysis of Pioneer Venus Mass Spectrometer Data are consistent with a water abundance of 30 ppm. Hodges and Tinsley found an escape flux due to charge exchange with hot H(+) of 2.8 x 10(exp 7) cm(exp -2) s(exp -1). Gurwell and Yung estimated an escape flux of 3.5 x 10(exp 6) cm(exp -2) s(exp -1) from collisions with hot O produced by dissociative recombination of O2(+). Brace et al. estimated an escape flux of 5 x 10(exp 6) cm(exp -2) s(exp -1) from ion escape from the ionotail of Venus. The combined estimated escape flux from all of these processes is 3.7 x 10(exp 7) cm(exp -2) s(exp -1), suggesting a lifetime against escape for water of less than 10(exp 8) years. A recent estimate of H escape flux employing a different ionospheric model and using Pioneer Venus reentry data to estimate the response of the escape flux to the solar cycle finds a somewhat lower escape flux of 1.4 x 10(exp 7) cm(exp -2) s(exp -1), suggesting a water lifetime closer to 2 x 10(exp 8) years, significantly less than the age of the planet. Large uncertainties remain in these quantities, yet the data suggest that a source of water more recent than primordial sources is required and that a steady-state is likely. To obvious candidates for this source water are cometary impact and volcanic outgassing. Other aspects of this investigation are discussed.

Grinspoon, David H.↗

Galacti chemical evolution: Hygrogen through zinc

Using the output from a grid of 60 Type II supernova models (Woosley & Weaver 1995) of varying mass (11 approx. less than (M/solar mass) approx. less than 40) and metallicity (0, 10(exp -4), 0.01, and 1 solar metallicity), the chemical evolution of 76 stable isotopes, from hydrogen to zinc, is calculated. The chemical evolution calculation employs a simple dynamical model for the Galaxy (infall with a 4 Gyr e-folding timescale onto a exponential dsk and 1/r(exp 2) bulge), and standard evolution parameters, such as a Salpeter initial mass function and a quadratic Schmidt star formation rate. The theoretical results are compared in detail with observed stellar abundances in stars with metallicities in the range -3.0 approx. less than (Fe/H) approx. less than 0.0 dex. While our discussion focuses on the solar neighborhood where there are the most observations, the supernova rates, an intrinsically Galactic quality, are also discussed.

Timmes, F. X.↗