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At least 1,027 records · Page 57

The effectiveness of TRIS and ammonium buffers in glass dissolution studies: a comparative analysis

Abstract Selecting appropriate buffers is crucial for evaluating the chemical durability of glass under controlled conditions such as in the EPA 1313 test designed to measure elemental release as a function of pH. The efficacy of two alkali-metal free buffers, TRIS (NH 2 C(CH 2 OH) 3 ) and ammonium chloride—ammonia (NH 3 /NH 4 Cl), was investigated during EPA 1313 testing of a simulated Hanford low-activity waste borosilicate glass in the alkaline regime (pH 8.5–10.5) at varying temperatures (RT, 40 °C, and 60 °C). While both buffers maintained the desired pH at room temperature, and up to 40 °C, the effectiveness of TRIS decreased at elevated temperatures, particularly at pH 10.5. Although 11 B NMR showed evidence of TRIS-B complexation, its effect on the rate of elemental release was found to be negligible under the test conditions. With ammonium buffer, the release of alkali cations was slightly elevated when compared to the same conditions with TRIS at early time points.

36 MATERIALS SCIENCE↗

Development of Countermeasures to Aid Functional Egress from the Crew Exploration Vehicle Following Long Duration Spaceflight

Astronauts experience disturbances in sensorimotor function following their return to Earth due to adaptive responses that occur during exposure to the microgravity conditions of space flight. As part of the Crew Exploration Vehicle design requirements, the crewmember adapted to the microgravity state may need to egress the vehicle within a few minutes for safety and operational reasons in various sea state conditions following a water landing. The act of emergency egress includes and is not limited to rapid motor control tasks (including both fine motor such as object manipulation and gross motor such as opening a hatch) and visual acuity tasks while maintaining spatial orientation and postural stability in time to escape safely. Exposure to even low frequency motions (0.2-2.0 Hz) induced by sea conditions surrounding a vessel can cause significant fine and gross motor control problems affecting critical functions. These motion frequencies coupled with the varying sea state conditions (frequencies ranging from 0.125-0.5 Hz) cause performance deficits by affecting the efficacy of motor and visual acuity dependent skills in tasks critical to emergency egress activities such as visual monitoring of displays, actuating discrete controls, operating auxiliary equipment and communicating with Mission Control and recovery teams. Thus, during exploration class missions the sensorimotor disturbances due to the crewmember's adaptation to microgravity may lead to disruption in the ability to maintain postural stability and perform functional egress tasks during the initial introduction to the Earth's gravitational environment. At present, the functional implication of the interactions between a debilitated crewmember during readaptation to Earth s gravity and the environmental constraints imposed by a water landing scenario is not defined and no operational countermeasure has been implemented to mitigate this risk. Stochastic resonance (SR) is a mechanism whereby noise can assist and hence enhance the response of neural systems to relevant, subthreshold sensory signals. Application of subthreshold stochastic resonance noise coupled to sensory input either through the proprioceptive, visual or vestibular sensory systems, has been shown to improve motor function. Crew members who have adapted to microgravity have acquired new sensorimotor strategies that take time to discard. We hypothesize that detection of time-critical subthreshold sensory signals will play a crucial role in improving strategic responses and thus the rate of skill re-acquisition will be faster, leading to faster recovery of function during their re-adaptation to Earth G. Therefore, we expect the use of stochastic resonance mechanisms will enhance the acquisition of new strategic abilities. This process should ensure rapid restoration of functional egress capabilities during the initial return to Earth G after prolonged space flight. Therefore, the overall goals of this project are to investigate performance of motor and visual tasks during varying sea state conditions and develop a countermeasure based on stochastic resonance that could be implemented to enhance sensorimotor capabilities with the aim of facilitating rapid adaptation to Earth s gravity, allowing rapid CEV egress on water in varying sea states following long-duration space flight.

Mulavara, Ajitkumar↗

NO x adsorption with CO and C 2 H 4 on Pd/SSZ-13: Experiments and modeling

A transient monolith model containing microkinetic schemes for NO uptake and release over Pd/SSZ-13 without and with reductants CO or C2H4 is presented. The scheme involves three cationic Pd species (Z – [PdOH] + , Z – Pd 2+ Z – , Z – Pd + ) as the active sites during uptake of NO, CO and C 2 H 4 , and their desorption and conversion at higher temperature. Kinetic parameters are estimated through a combination of density functional theory (DFT) estimates and a fit of uptake, desorption and conversion data. The tuned model is validated at different uptake temperatures, ramp rates, and flowrates. A “degree of uptake control” parameter is defined that helps to identify the step(s) that are uptake controlling. The model helps to interpret the data features and is used to identify operating conditions to meet application-relevant performance metrics, including NO trapping efficiency and NO release temperature. Furthermore, the model demonstrates higher NO uptake on Pd/SSZ-13 compared to Pd/ZSM-5.

42 ENGINEERING↗

Factors Influencing Pulmonary Toxicity in Children Undergoing Allogeneic Hematopoietic Stem Cell Transplantation in the Setting of Total Body Irradiation-Based Myeloablative Conditioning

Purpose: This study evaluated factors associated with increased risk of pulmonary toxicity (PT) from any cause in pediatric patients after myeloablative conditioning, using total body irradiation (TBI), followed by allogeneic hematopoietic stem cell transplantation (HSCT). Methods and Materials: The records of 129 consecutive pediatric patients (range: 1-21 years of age) who underwent TBI-based myeloablative conditioning for hematologic malignancies at our institution between January 2003 and May 2014 were reviewed. Although total TBI doses ranged from 10.5 to 14 Gy, lung doses were limited to 10 Gy with partial transmission blocks. TBI dose rates ranged from 5.6 cGy/min to 20.9 cGy/min. PT was classified using clinical symptoms, radiographic evidence, and ventilatory defects on pulmonary function tests. Noninfectious (idiopathic) pneumonia syndrome (IPS) was characterized by patients exhibiting PT while demonstrating no signs of infection throughout the follow-up period. Results: PT from any cause developed in 70.5% of patients and was significantly associated with increased transplantation-related mortality (TRM) (P=.03) and decreased overall survival (OS) (P=.02). IPS developed in 23.3% of patients but was not associated with increased TRM (P=.6) or decreased OS (P=.5). Acute graft-versus-host disease (GVHD) significantly affected PT (P=.001) but did not significantly influence the development of IPS (P=.4). Infection was a leading cause of PT (75.8%). TBI dose rate significantly affected development of overall PT (P=.02) and was the sole factor to significantly influence the incidence of IPS (P=.002). TBI total dose, dose per fraction, disease type, transplantation chemotherapy, age of patient, sex, and donor type did not significantly impact overall PT or IPS. Conclusions: A high incidence of PT was noted in this large series of homogeneously treated pediatric patients undergoing TBI for allogeneic HSCT. TBI dose rates affected overall PT and strongly influenced IPS. TBI dose rate is a contributing factor influencing pulmonary toxicity and rates less than 15 cGy/min should be considered to decrease the risk of IPS.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

A stress-induced source of phonon bursts and quasiparticle poisoning

Abstract The performance of superconducting qubits is degraded by a poorly characterized set of energy sources breaking the Cooper pairs responsible for superconductivity, creating a condition often called “quasiparticle poisoning”. Both superconducting qubits and low threshold dark matter calorimeters have observed excess bursts of quasiparticles or phonons that decrease in rate with time. Here, we show that a silicon crystal glued to its holder exhibits a rate of low-energy phonon events that is more than two orders of magnitude larger than in a functionally identical crystal suspended from its holder in a low-stress state. The excess phonon event rate in the glued crystal decreases with time since cooldown, consistent with a source of phonon bursts which contributes to quasiparticle poisoning in quantum circuits and the low-energy events observed in cryogenic calorimeters. We argue that relaxation of thermally induced stress between the glue and crystal is the source of these events.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Stellar influence on heavy ion escape from unmagnetized exoplanets

Abstract Planetary habitability is in part determined by the atmospheric evolution of a planet; one key component of such evolution is escape of heavy ions to space. Ion-loss processes are sensitive to the plasma environment of the planet, dictated by the stellar wind and stellar radiation. These conditions are likely to vary from what we observe in our own Solar system when considering a planet in the habitable zone around an M-dwarf. Here, we use a hybrid global plasma model to perform a systematic study of the changing plasma environment and ion escape as a function of stellar input conditions, which are designed to mimic those of potentially habitable planets orbiting M-dwarfs. We begin with a nominal case of a solar wind experienced at Mars today, and incrementally modify the interplanetary magnetic field orientation and strength, dynamic pressure, and Extreme Ultraviolet input. We find that both ion-loss morphology and overall rates vary significantly, and in cases where the stellar wind pressure was increased, the ion loss began to be diffusion or production limited with roughly half of all produced ions being lost. This limit implies that extreme care must be taken when extrapolating loss processes observed in the Solar system to extreme environments.

79 ASTRONOMY AND ASTROPHYSICS↗

Characterizing the impact of particle behavior at fracture intersections in three-dimensional discrete fracture networks

We characterize the influence of different intersection mixing rules for particle tracking simulations on transport properties through three-dimensional discrete fracture networks. It is too computationally burdensome to explicitly resolve all fluid dynamics within a large three-dimensional fracture network. In discrete fracture network (DFN) models, mass transport at fracture intersections is modeled as a subgrid scale process based on a local Péclet number. The two most common mass transfer mixing rules are (1) complete mixing, where diffusion dominates mass transfer, and (2) streamline routing, where mass follows pathlines through an intersection. Although it is accepted that mixing rules impact local mass transfer through single intersections, the effect of the mixing rule on transport at the fracture network scale is still unresolved. Through the use of explicit particle tracking simulations, we study transport through a quasi-two-dimensional lattice network and a three-dimensional network whose fracture radii follow a truncated power-law distribution. We find that the impact of the mixing rule is a function of the initial particle injection condition, the heterogeneity of the velocity field, and the geometry of the network. Furthermore, our particle tracking simulations show that the mixing rule can particularly impact concentrations on secondary flow pathways. As a result, we relate these local differences in concentration to reactive transport and show that streamline routing increases the average mixing rate in DFN simulations.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

A Hydropower Biological Evaluation Toolset (HBET) for Characterizing Hydraulic Conditions and Impacts of Hydro-Structures on Fish

Currently, approximately 16% of the world’s electricity and over 80% of the world’s renewable electricity is generated from hydropower resources, and there is potential for development of a significant amount of new hydropower capacity. However, in practice, realizing all the potential hydropower resource is limited by various factors, including environmental effects and related mitigation requirements. That is why hydropower regulatory requirements frequently call for targets to be met regarding fish injury and mortality rates. Hydropower Biological Evaluation Toolset (HBET), an integrated suite of software tools, is designed to characterize hydraulic conditions of hydropower structures and provide quantitative estimates of fish injury and mortality rates due to various physical stressors including strike, pressure, and shear. HBET enables users to design new studies, analyze data, perform statistical analyses, and evaluate biological responses. In this paper, we discuss the features of the HBET software and describe a case study that illustrates its functionalities. Here, HBET can be used by turbine manufacturers, hydropower operators, and regulators to design and operate hydropower systems that minimize ecological impacts in a cost-effective manner.

13 HYDRO ENERGY↗

Analysis of the passive stabilization of the long duration exposure facility

The nominal Long Duration Exposure Facility (LDEF) configurations and the anticipated orbit parameters are presented. A linear steady state analysis was performed using these parameters. The effects of orbit eccentricity, solar pressure, aerodynamic pressure, magnetic dipole, and the magnetically anchored rate damper were evaluated to determine the configuration sensitivity to variations in these parameters. The worst case conditions for steady state errors were identified, and the performance capability calculated. Garber instability bounds were evaluated for the range of configuration and damping coefficients under consideration. The transient damping capabilities of the damper were examined, and the time constant as a function of damping coefficient and spacecraft moment of inertia determined. The capture capabilities of the damper were calculated, and the results combined with steady state, transient, and Garber instability analyses to select damper design parameters.

Siegel, S. H.↗

The investigation of tethered satellite system dynamics

Progress in tethered satellite system dynamics research is reported. A retrieval rate control law with no angular feedback to investigate the system's dynamic response was studied. The initial conditions for the computer code which simulates the satellite's rotational dynamics were extended to a generic orbit. The model of the satellite thrusters was modified to simulate a pulsed thrust, by making the SKYHOOK integrator suitable for dealing with delta functions without loosing computational efficiency. Tether breaks were simulated with the high resolution computer code SLACK3. Shuttle's maneuvers were tested. The electric potential around a severed conductive tether with insulator, in the case of a tether breakage at 20 km from the Shuttle, was computed. The electrodynamic hazards due to the breakage of the TSS electrodynamic tether in a plasma are evaluated.

Lorenzini, E.↗

Calculations and experiments concerning lifting force and power in TEMPUS

A critical comparison is reported between the theoretically predicted and experimentally measured values for the electromagnetic lifting force and the heating rates which may be achieved, under simulated microgravity conditions, using the TEMPUS electromagnetic levitation device. The experiments involved the suspending of a metallic sample from one arm of a recording balance, such that it was carefully positioned between the heating and the positioning coils of the levitation device. The net force exerted by the sample was measured as a function of position, the coil currents, and the nature of the sample. Some calculations are also reported regarding the power absorption by the sample. The theoretical predictions, based on the numerical solution of Maxwell's equations using the volume integral technique, were found to be in excellent agreement with the measurements. For the idealized case of a spherical sample, analytical solutions describing the lifting force were also found to agree very well with the computed results.

Zong, J. H.↗

Speed tuning of motion segmentation and discrimination

Motion transparency requires that the visual system distinguish different motion vectors and selectively integrate similar motion vectors over space into the perception of multiple surfaces moving through or over each other. Using large-field (7 degrees x 7 degrees) displays containing two populations of random-dots moving in the same (horizontal) direction but at different speeds, we examined speed-based segmentation by measuring the speed difference above which observers can perceive two moving surfaces. We systematically investigated this 'speed-segmentation' threshold as a function of speed and stimulus duration, and found that it increases sharply for speeds above approximately 8 degrees/s. In addition, speed-segmentation thresholds decrease with stimulus duration out to approximately 200 ms. In contrast, under matched conditions, speed-discrimination thresholds stay low at least out to 16 degrees/s and decrease with increasing stimulus duration at a faster rate than for speed segmentation. Thus, motion segmentation and motion discrimination exhibit different speed selectivity and different temporal integration characteristics. Results are discussed in terms of the speed preferences of different neuronal populations within the primate visual cortex.

NASA Center ARC↗

Particle Acceleration in Dissipative Pulsar Magnetospheres

Pulsar magnetospheres represent unipolar inductor-type electrical circuits at which an EM potential across the polar cap (due to the rotation of their magnetic field) drives currents that run in and out of the polar cap and close at infinity. An estimate ofthe magnitude of this current can be obtained by dividing the potential induced across the polar cap V approx = B(sub O) R(sub O)(Omega R(sub O)/c)(exp 2) by the impedance of free space Z approx eq 4 pi/c; the resulting polar cap current density is close to $n {GJ} c$ where $n_{GJ}$ is the Goldreich-Julian (GJ) charge density. This argument suggests that even at current densities close to the GJ one, pulsar magnetospheres have a significant component of electric field $E_{parallel}$, parallel to the magnetic field, a condition necessary for particle acceleration and the production of radiation. We present the magnetic and electric field structures as well as the currents, charge densities, spin down rates and potential drops along the magnetic field lines of pulsar magnetospheres which do not obey the ideal MHD condition $E cdot B = 0$. By relating the current density along the poloidal field lines to the parallel electric field via a kind of Ohm's law $J = sigma E_{parallel}$ we study the structure of these magnetospheres as a function of the conductivity $sigma$. We find that for $sigma gg OmegaS the solution tends to the (ideal) Force-Free one and to the Vacuum one for $sigma 11 OmegaS. Finally, we present dissipative magnetospheric solutions with spatially variable $sigma$ that supports various microphysical properties and are compatible with the observations.

Kazanas, Z.↗

Hot deformation behaviors and processing maps of B{sub 4}C/Al6061 neutron absorber composites

In this study, the hot deformation behaviors of 30 wt.% B{sub 4}C/Al6061 neutron absorber composites (NACs) have been investigated by conducting isothermal compression tests at temperatures ranging from 653 K to 803 K and strain rates from 0.01 to 10 s{sup −1}. It was found that, during hot compression, the B{sub 4}C/Al6061 NACs exhibited a steady flow characteristic which can be expressed by the Zener-Hollomon parameter as a hyperbolic-sine function of flow stress. High average activation energy (185.62 kJ/mol) of B{sub 4}C/Al6061 NACs is noted in current study owing to the high content of B{sub 4}C particle. The optimum hot working conditions for B{sub 4}C/Al6061 NACs are found to be 760–803 K/0.01–0.05 s{sup −1} based on processing map and microstructure evolution. Typical material instabilities are thought to be attributed to void formation, adiabatic shear bands (ASB), particle debonding, and matrix cracking. Finally, the effect of the plastic deformation zones (PDZs) on the microstructure evolution in this 30 wt.% B{sub 4}C/Al6061 composite is found to be very important. - Highlights: •The hot deformation behavior of the 30 wt.% B{sub 4}C/Al6061 NACs was first analyzed. •The 3D efficiency map and the instability map are developed. •The optimum hot working conditions were identified and validated by SEM and TEM. •The hot deformation schematic diagram of 30 wt.% B{sub 4}C/Al6061 NACs is developed.

36 MATERIALS SCIENCE↗

Magnetic Properties of Electroformed Ni and Ni-Fe for Micromagnetic MEMS Applications

This paper reports a new technique which is based on electroforming process for high permeability Ni and Ni-Fe alloy. The magnetic properties of Ni and Ni-Fe alloy are investigated as a function of plating current density via scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), and vibrating sample magnetometer (VSM). Concentration-dependent kinetics is used to formulate the deposition rate and also the same is verified by using finite element analysis tool COMSOL Multiphysics. Several experiments are performed to derive the relation between electroplating parameters and magnetic properties. The process conditions are optimized to develop high permeability (∼16000) Ni-Fe alloy (85.71–14.29 %). The higher current density shows a monotonically increasing behavior of relative permeability (μ{sub r}). In addition, the B-H curves indicate that the saturation magnetization (B{sub sat}) increases and coercivity decreases with increasing plating current density. Our experimental data confirms that the higher current density increase the softness of Ni. The observed properties of Ni and Ni-Fe based on experimental results can be used to study the magnetic behavior of micromagnetic sensors and large force actuators.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mass Spectral Detection of Forward- and Reverse-Hydrogen/Deuterium Exchange Resulting from Residual Solvent Vapors in Electrospray Sources

Characterizing glycans is analytically challenging since glycans are heterogeneous, branched polymers with different three-dimensional conformations. Hydrogen/deuterium exchange-mass spectrometry (HDX-MS) has been used to analyze native conformations and dynamics of biomolecules by measuring the mass increase of analytes as labile protons are replaced with deuterium following exposure to deuterated solvents. The rate of exchange is dependent on the chemical functional group, the presence of hydrogen bonds, pH, temperature, charge, and solvent accessibility. HDX-MS of carbohydrates is challenging due to the rapid exchange rate of hydroxyls. Here, we describe an observed HDX reaction associated with residual solvent vapors saturating electrospray sources. When undeuterated melezitose was infused after infusing D{sub 2}O, samples with up to 73% deuterium exchange were detected. This residual solvent HDX was observed for both carbohydrates and peptides in multiple instruments and dependent on sample infusion rate, infusion time, and deuterium content of the solvent. This residual solvent HDX was observed over several minutes of sample analysis and persisted long enough to alter the measured deuterium labeling and possibly change the interpretation of the results. This work illustrates that residual solvent HDX competes with in-solution HDX for rapidly exchanging functional groups. Thus, we propose conditions to minimize this effect, specifically for top-down, in-electrospray ionization, and quench-flow HDX experiments. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Expression Patterns of Energy-Related Genes in Single Cells Uncover Key Isoforms and Enzymes That Gain Priority Under Nanoparticle-Induced Stress

Cellular responses to nanoparticles (NPs) have been largely studied in cell populations, providing averaged values that often misrepresent the true molecular processes that occur in the individual cell. To understand how a cell redistributes limited molecular resources to achieve optimal response and survival requires single-cell analysis. Here we applied multiplex single molecule-based fluorescence in situ hybridization (fliFISH) to quantify the expression of 10 genes simultaneously in individual intact cells, including glycolysis and glucose transporter genes, which are critical for restoring and maintaining energy balance. We focused on individual gill epithelial cell responses to lithium cobalt oxide (LCO) NPs, which are actively pursued as cathode materials in lithium-ion batteries, raising concerns about their impact on the environment and human health. We found large variabilities in the expression levels of all genes between neighboring cells under the same exposure conditions, from only a few transcripts to over 100 copies in individual cells. Gene expression ratios among the 10 genes in each cell uncovered shifts in favor of genes that play key roles in restoring and maintaining energy balance. Among these genes are isoforms that can secure and increase glycolysis rates more efficiently, as well as genes with multiple cellular functions, in addition to glycolysis, including DNA repair, regulation of gene expression, cell cycle progression, and proliferation. Our study uncovered prioritization of gene expression in individual cells for restoring energy balance under LCO NP exposures. Broadly, our study gained insight into single-cell strategies for redistributing limited resources to achieve optimal response and survival under stress.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio, revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.

BINDING↗