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At least 829 records · Page 46

Design of a Family of Mars Chemical Transportation Elements

NASA’s Mars Architecture Team (MAT) has recently developed a collection of concepts to assess the capabilities and constraints presented by architectures incorporating large-scale Mars In-Situ Resource Utilization (ISRU) propellant production. The focus of this manuscript is on the concept design of chemical propellant-based transportation systems including a dual role lander/ascent vehicle and an in-space transporter. Mission performance analyses performed during a recent design analysis cycle derived the 300,000 kg propellant production capacity utilized for preliminary concept designs of enabling surface ISRU systems, power systems, fluid handling systems, and their concept of operation, detailed in companion papers.

Mars↗

Design of a Family of Mars Chemical Transportation Elements

NASA’s Mars Architecture Team (MAT) has recently developed a collection of concepts to assess the capabilities and constraints presented by architectures incorporating large-scale Mars In-Situ Resource Utilization (ISRU) propellant production. The focus of this manuscript is on the concept design of chemical propellant-based transportation systems including a dual role lander/ascent vehicle and an in-space transporter. Mission performance analyses performed during a recent design analysis cycle derived the 300,000 kg propellant production capacity utilized for preliminary concept designs of enabling surface ISRU systems, power systems, fluid handling systems, and their concept of operation, detailed in companion papers.

Mars↗

Complex Sources and Impacts on Remediation and Monitoring Approaches

Remedy selection, implementation, and coordination with tank farm activities for adjacent waste sites need to be facilitated by a technically defensible description of sources and their relative strength and temporal contributions to groundwater contamination. Detailed data describing contaminant source releases are typically not available, so source locations are highly uncertain. Furthermore, data on sources and model parameters are not readily available through direct measurements. Instead, source data are often derived by extrapolation from a few direct and/or indirect measurements, while model parameters are commonly estimated using inverse modeling or calibration methods. Because the conceptual model of sources will influence the mass and timing of the flux of contaminants to groundwater, uncertainty in the source terms should be considered. Even though a best-fit model can often be identified, it may not be the best representation of the sources given the sparse, uncertain nature of the data used for estimating source terms. To support future feasibility studies, a systematic approach is needed for identifying remediation and monitoring activities appropriate under conditions of uncertainty. In this study, an integrated assessment of alternative conceptual model elements has been examined using the B-Complex site in the Hanford Central Plateau to demonstrate how multiple sources in a waste management complex can be described to identify their relative contributions to groundwater. The heterogeneous structure of the system is modeled based on available field information on the lithological data for both the vadose zone and aquifer. The approach includes a simulation assessment and linkages to site data, with an uncertainty analysis applied to evaluate the effects of source term uncertainty on contaminant mass flux to groundwater. An integrated assessment of alternative conceptual model elements was evaluated to identify how parameter uncertainty impacts both temporal and spatial uncertainties associated with vadose zone source terms. Modeling scenarios identify important characteristics of remediation target zones to provide context for how surface barriers, in situ remedies, and water-table treatment zones can be designed to account for source dynamics. Ramifications for remediation and monitoring are discussed within the context of the source term uncertainty. The described approach facilitates systematically addressing alternative conceptual model questions in relation to remediation and monitoring and supports the remedial investigation/ feasibility study process and the remediation strategy development for the Hanford Central Plateau.

Rockhold, Mark L.↗

Complex Sources and Impacts on Remediation and Monitoring Approaches - 19058

Remedy selection, implementation, and coordination with tank farm activities for adjacent waste sites need to be facilitated by a technically defensible description of sources and their relative strength and temporal contributions to groundwater contamination. Detailed data describing contaminant source releases are typically not available, so source locations are highly uncertain. Furthermore, data on sources and model parameters are not readily available through direct measurements. Instead, source data are often derived by extrapolation from a few direct and/or indirect measurements, while model parameters are commonly estimated using inverse modeling or calibration methods. Because the conceptual model of sources will influence the mass and timing of the flux of contaminants to groundwater, uncertainty in the source terms should be considered. Even though a best-fit model can often be identified, it may not be the best representation of the sources given the sparse, uncertain nature of the data used for estimating source terms. To support future feasibility studies, a systematic approach is needed for identifying remediation and monitoring activities appropriate under conditions of uncertainty. In this study, an integrated assessment of alternative conceptual model elements has been examined using the B-Complex site in the Hanford Central Plateau to demonstrate how multiple sources in a waste management complex can be described to identify their relative contributions to groundwater. The heterogeneous structure of the system is modeled based on available field information on the lithological data for both the vadose zone and aquifer. The approach includes a simulation assessment and linkages to site data, with an uncertainty analysis applied to evaluate the effects of source term uncertainty on contaminant mass flux to groundwater. An integrated assessment of alternative conceptual model elements was evaluated to identify how parameter uncertainty impacts both temporal and spatial uncertainties associated with vadose zone source terms. Modeling scenarios identify important characteristics of remediation target zones to provide context for how surface barriers, in situ remedies, and water-table treatment zones can be designed to account for source dynamics. Ramifications for remediation and monitoring are discussed within the context of the source term uncertainty. The described approach facilitates systematically addressing alternative conceptual model questions in relation to remediation and monitoring and supports the remedial investigation/ feasibility study process and the remediation strategy development for the Hanford Central Plateau. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Is Mars Sample Return Required Prior to Sending Humans to Mars?

Prior to potentially sending humans to the surface of Mars, it is fundamentally important to return samples from Mars. Analysis in Earth's extensive scientific laboratories would significantly reduce the risk of human Mars exploration and would also support the science and engineering decisions relating to the Mars human flight architecture. The importance of measurements of any returned Mars samples range from critical to desirable, and in all cases these samples will would enhance our understanding of the Martian environment before potentially sending humans to that alien locale. For example, Mars sample return (MSR) could yield information that would enable human exploration related to 1) enabling forward and back planetary protection, 2) characterizing properties of Martian materials relevant for in situ resource utilization (ISRU), 3) assessing any toxicity of Martian materials with respect to human health and performance, and 4) identifying information related to engineering surface hazards such as the corrosive effect of the Martian environment. In addition, MSR would be engineering 'proof of concept' for a potential round trip human mission to the planet, and a potential model for international Mars exploration.

biohazards↗

In Situ Characterization of Surface Recombination in p-Si/SiO x Based Photoelectrochemical Cells

Time-resolved infrared (TRIR) and electrochemical impedance spectroscopy (EIS) were utilized to quantify surface states present at silicon oxide (SiO x ) protected crystalline p-Si electrolyte interfaces. The primary goal was to identify p-Si/SiO x photoelectrodes with both low surface recombination rates and efficient multi-electron transfer to an acceptor present in the external electrolyte. Three SiO x layers were investigated: native oxide (nOx), chemical oxide (cOx), and rapid thermal annealed (RTA) thermal oxide (tOx). Comparative study with [Ru(bpy) 3 ](PF 6 ) 2 as the electron acceptor indicated that tOx was most optimal with a small effective recombination rate, multi-electron transfer capability, and photovoltage of 500 ± 50 mV. A secondary goal was to analyze the surface recombination rates with the Shockley–Read–Hall (SRH) kinetic model. Two surface states were identified from this analysis, one closer to the CB edge (V t,1 ) and the other near the midgap (V t,2 ). EIS and SRH analyses revealed that a forming gas (5% H 2 /N 2 ) anneal (FGA) decreased surface recombination for tOx and nOx through a lower density of surface states. In the case of tOx, the infrared data indicated that V t,2 was completely removed. Here, the energetic positions of the band edges were correlated with the surface state density; low densities corresponded to more favorable potentials for inversion layer formation, which is expected to be most optimal for photocatalysis. Collectively this study indicates that the free carrier dynamics provided by TRIR represent a powerful in situ probe of the band edge and the surface state energetics in silicon based photoelectrochemical cells.

Electrochemical Impedance Spectroscopy↗

Ni5Ga3 Catalysts for CO2 Reduction to Methanol: Exploring the Role of Ga Surface Oxidation/reductions on Catalytic Activity

Ad-Ni5Ga3/SiO2 catalyst, which is highly active and stable for thermal CO2 hydrogenation to methanol, was investigated to understand its surface dynamics during reaction conditions. The catalyst was prepared, tested and characterized using a multitude of techniques, including ex-situ XRD, TEM, H2-TPR, CO chemisorption and in-situ ETEM and APXPS. The formation of Ga2O3 upon air exposure was observed and the consequences on catalytic activity were investigated. Results revealed that upon air exposure Ga migrates from the subsurface region to the surface of the nanoparticles forming a Ga-oxide shell surrounding a metallic core. The oxide shell can be reduced completely at high temperatures and the temperature of the reduction activation treatment plays a crucial role on the catalytic activity. This air exposure-reduction procedure results in a redistribution of the Ga species in the surface/subsurface region, promoted by a higher Ga affinity for oxygen. XRD analysis of the post-reaction samples provide evidence for the partial transformation of a Ni5Ga3 intermetallic phase into a Ni-rich Ni3Ga phase. APXPS data indicate that the Ni-rich phase forms in the subsurface region. A Ga-rich phase exists on the surface, where the Ni/Ga ratio reaches 2/3 upon activation in hydrogen. At low reduction temperatures an amorphous Ga2O3 shell remains, indicating a promotion effect on methanol synthesis activity.

Ni-Ga, intermetallic, methanol synthesis, in-situ ↗

Nanoscale Perspectives of Metal Degradation via In Situ Atom Probe Tomography

Abstract We report a unique in situ instrument development effort dedicated to studying gas/solid interactions relevant to heterogeneous catalysis and early stages of oxidation of materials via atom probe tomography and microscopy (APM). An in situ reactor cell, similar in concept to other reports, has been developed to expose nanoscale volumes of material to reactive gas environments, in which temperature, pressure, and gas chemistry are well controlled. We demonstrate that the combination of this reactor cell with APM techniques can aid in building a better mechanistic understanding of resultant composition and surface and subsurface structure changes accompanying gas/surface reactions in metal and metal alloy systems through a series of case studies: O 2 /Rh, O 2 /Co, and O 2 /Zircaloy-4. In addition, the basis of a novel operando mode of analysis within an atom probe instrument is also reported. The work presented here supports the implementation of APM techniques dedicated to atomic to near-atomically resolved gas/surface interaction studies of materials broadly relevant to heterogeneous catalysis and oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen accumulation in and at the perimeter of U–C–N–O inclusions in uranium – A SIMS analysis

We use imaging secondary ion mass spectrometry (SIMS) with a Cameca NanoSIMS 50 to determine the distribution and relative concentration of H in two uranium metal samples: sample1(LANL), as cast with less than 1 wppm H, sample2(Y12), outgassed 6 h in vacuum at 630 °C to remove hydrogen. H ion counts appear almost exclusively associated with ‘carbide’ inclusions, based on H – , C – and O – ion images for uranium surfaces sputter-cleaned in situ with a 16 keV Cs + ion beam. Here, two classes of inclusions are identified: small, micrometer to sub-micrometer inclusions and larger, clearly angular inclusion (≥3 μm). In sample1(LANL) the large inclusions (≥250/mm 2 ) show a low H – /C – ratio inside, and have H – /C – ratios at their perimeters comparable in magnitude to that seen in μm-size inclusions. Small inclusions (~2500/mm 2 ) contain H more uniformly throughout and, averaged over the inclusion, the small inclusions have approximately 50 times higher relative H concentration than the large inclusions. Sample2(Y12) was found to have comparable H – /C – ratios in the large carbides, but no small inclusions were observed. Because of the matrix-sensitivity of SIMS, H/C ratios representing the actual composition of the inclusions cannot be derived from the H – /C – ratios without calibration UC samples with known H content, which are not currently available.

36 MATERIALS SCIENCE↗

Insights into Copper Sulfide Formation from Cu and S K edge XAS and DFT studies

An understanding of the fundamentals of the reaction between CuO with trace amounts of H 2 S to form CuS products is critical for the optimal utilization of this process in sulfur removal applications. Unfortunately, CuS is a complex material, featuring various Cu 2-x S compounds (with 0 ≤ x ≤ 1), distorted crystal phases, and varying electronic structures and coordination environments of Cu and S ions. In this work, we combine ex situ and in situ X-ray absorption spectroscopy (XAS) at S and Cu K edges, fixed bed sorption experiments, DFT simulations, and other characterization techniques to speciate the CuS products formed at different temperatures (298–383 K) and from CuO sorbents with different crystallite sizes (2.8–40 nm). The results of our analysis identify the formation of a distorted CuS layer at the surface of CuO crystals with disulfide groups with shorter Cu–S bonds and higher delocalization of the positive charge of the Cu center into (S 1– )2. This distorted CuS layer dominates the XAS signal at lower temperatures (298–323 K) and at the initial stages of sulfidation at higher temperatures (353 and 383 K) where conversion is low (<40%). First-principles atomistic simulations confirm the thermodynamic favorability of the formation of surface (S 1– )2 on both CuO (111) and ($\bar{1}11$) surfaces, providing further support for our experimental observations. Furthermore, these simulations reveal that the presence of disulfide bonds stabilized surface hydroxyl groups, leading to lower Gibbs Free Energies of their surface migration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Potentiometric and electrokinetic signatures of iron(II) interactions with (a,y)-Fe2O3

The role of surface electrostatics on the reductive dissolution of iron (III) oxides is poorly understood, despite its importance in controlling the amount of mobilized iron. We report the potentiometric titration of the a; y -Fe2O3 oxides exposed to reductants and complexing ligands (Fe(II), ascorbate, oxalate, malonate). We monitored in situ surface and potentials, the ratio of mobilized ferric to ferrous ions, and periodically analyzed nanoparticle crystal structure using X-ray diffraction. We found that addition of Fe2+ ions produces a response consistent with the iron solubilityactivity curve, whereas the presence of ascorbate significantly decreases the amount of mobilized Fe(III) due to reduction to Fe(II). In addition, XRD analysis proved that y-Fe2O3 particles remain structurally unchanged along the titration pathway despite iron cycling between aqueous and solid reservoirs. Our studies, suggest that the surface redoxactivity of iron oxides is primarily governed by the balance between Fe(III) and Fe(II) ions in aqueous phase, which may be easily altered by complexing and reducing agents.

Toczydlowska, Diana↗

The near-nucleus gas coma of comet 67P/Churyumov-Gerasimenko prior to the descent of the surface lander PHILAE

Context. The European Space Agency (ESA) Rosetta mission was the most comprehensive study of a comet ever performed. In particular, the Rosetta orbiter, which carried many instruments for monitoring the evolution of the dusty gas emitted by the cometary nucleus, returned an enormous volume of observational data collected from the close vicinity of the nucleus of comet 67P/Churyumov-Gerasimenko. Aims. Such data are expected to yield unique information on the physical processes of gas and dust emission, using current physical model fits to the data. We present such a model (the RZC model) and our procedure of adjustment of this model to the data. Methods. The RZC model consists of two components: (1) a numerical three-dimensional time-dependent code solving the Eulerian/Navier-Stokes equations governing the gas outflow, and a direct simulation Monte Carlo (DSMC) gaskinetic code with the same objective; and (2) an iterative procedure to adjust the assumed model parameters to best-fit the observational data at all times. Results. We demonstrate that our model is able to reproduce the overall features of the local neutral number density and composition measurements of Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) Comet Pressure Sensor (COPS) and Double Focusing Mass Spectrometer (DFMS) instruments in the period August 1–November 30, 2014. The results of numerical simulations show that illumination conditions on the nucleus are the main driver for the gas activity of the comet. We present the distribution of surface inhomogeneity best-fitted to the ROSINA COPS and DFMS in situ measurements.

79 ASTRONOMY AND ASTROPHYSICS↗

A digital holography ex situ measurement characterization of plasma-exposed surface erosion from an electrothermal arc source

Digital holography has been proposed to fulfill a need for an imaging diagnostic capable of in situ monitoring of surface erosion caused by plasma–material interaction in nuclear fusion devices. A digital holography diagnostic for 3D surface erosion measurement has been developed at Oak Ridge National Laboratory with the goal of deployment on a plasma device. A proof-of-concept in situ demonstration is planned which would involve measurement of plasma erosion on targets exposed to an electrothermal arc source. This work presents the results of an ex situ characterization of the capability and limitations of holographic imaging of targets exposed to the arc source. Targets were designed to provide a fiducial for comparison of deformed and unaffected areas. The results indicated that the average net erosion was ~150 nm/plasma exposure, which is expected to be within the diagnostic’s measurement capacity. Surface roughness averages determined by holographic image analysis showed good agreement with measurements taken with a profilometer. Finally, the limit of the holography diagnostic’s x–y spatial resolution was characterized by comparison with scanning electron microscope imaging.

47 OTHER INSTRUMENTATION↗

Pulsed Airborne Lidar Measurements of Atmospheric CO2 Column Absorption and Line Shapes from 3-13 km Altitudes

We have developed a pulsed lidar technique for measuring the tropospheric CO2 concentrations as a candidate for NASA's planned ASCENDS space mission. Our technique uses two pulsed laser transmitters allowing simultaneous measurement of a CO2 absorption line in the 1570 nm band, O2 extinction in the Oxygen A-band and surface height and backscatter. The lidar measures the energy and time of flight of the laser echoes reflected from the atmosphere and surface. The lasers are rapidly and precisely stepped in wavelength across the CO2 line and an O2 line region during the measurement. The direct detection receiver uses a telescope and photon counting detectors, and measures the background light and energies of the laser echoes from the surface along with scattering from any aerosols in the path. The gas extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on- and off- line signals via the DIAL technique. Time gating is used to isolate the laser echo signals from the surface, and to reject laser photons scattered in the atmosphere. The time of flight of the laser pulses are also used to estimate the height of the scattering surface and to identify cases of mixed cloud and ground scattering. We have developed an airborne lidar to demonstrate the CO2 measurement from the NASA Glenn Lear-25 aircraft. The airborne lidar steps the pulsed laser's wavelength across the selected CO2 line with 20 steps per scan. The line scan rate is 450 Hz, the laser pulse widths are 1 usec, and laser pulse energy is 24 uJ. The time resolved laser backscatter is collected by a 20 cm telescope, detected by a photomultiplier and is recorded by a photon counting system. We made initial airborne measurements on flights during fall 2008. Laser backscatter and absorption measurements were made over a variety of land and water surfaces and through thin clouds. The atmospheric CO2 column measurements using the 1572.33 nm CO2 lines. Two flights were made above the US Department of Energy's (DOE) SGP ARM site at altitudes from 3-8 km. These flights were coordinated with DOE investigators who flew an in-situ CO2 sensor on a Cessna aircraft under the path. The increasing CO2 line absorptions with altitudes were evident and comparison with in-situ measurements showed agreements to 6 ppm. In spring 2009 we improved the aircraft's nadir window and during July and August we made 9 additional 2 hour long flights and measured the atmospheric CO2 absorption and line shapes using the 1572.33 nm CO2 line. Measurements were made at stepped altitudes from 3-13 km over a variety of surface types in Nebraska, Illinois, the SGP ARM site, and near and over the Chesapeake Bay in North Carolina and eastern Virginia. Strong laser signals and clear CO2 line shapes were observed at all altitudes, and some measurements were made through thin clouds. The flights over the ARM site were underflown with in-situ measurements made from the DOE Cessna. Analysis shows that the average signal levels follow predicted values, the altimetry measurements had an uncertainty of about 4 m, and that the average optical line depths follow the number density calculated from in-situ sensor readings. The Oklahoma and east coast flights were coordinated with a LaRC/ITT CO2 lidar on the LaRC UC-12 aircraft, a LaRC in-situ CO2 sensor, and the Oklahoma flights also included a JPL CO2 lidar on a Twin Otter aircraft. More details of the flights, measurements, analysis and scaling to space will be described in the presentation.

Abshire, James↗

A Study of the Kinematic and Dynamic Processes associated with Mesoscale Snowbands in a Midwest United States Snowstorm on 5 February 2020

Mesoscale snowbands are frequently responsible for dumping large amounts of snow over a relatively small region and pose a considerable forecasting challenge. The present study focuses on the mesoscale snowbands observed on 5 February 2020 over the Midwest United States. In order to improve the forecasting of mesoscale snowbands, it is important to understand the processes that organize these features. To this end, we are investigating the kinematic and dynamic processes that shape the mesoscale snowbands using a combination of high-altitude airborne radar, in-situ aircraft measurements, surface observations, and model simulations. This presentation will primarily focus on the three-dimensional structure of the mesoscale snowbands in terms of EXRAD reflectivity and horizontal winds. The horizontal winds are retrieved from the EXRAD scanning-beam Doppler velocities using a VAD technique. These winds, in combination with virtual potential temperature taken from the HRRR operational analysis, are used to compute the bulk Richardson number in order to investigate any contributions to banding features that might be tied to Kelvin-Helmholtz instability. Our analysis does not support the presence of Kelvin-Helmholtz instability. That said, low, but not subcritical, Richardson numbers were found near the top of some banding features in this event and it is possible that the model analysis is smoothing out the virtual potential temperature fields. Finally, we present arguments for using a flight module designed to sample the along-band structures with particular emphasis on observing generating cells and low-level microphysics.

Charles N. Helms↗

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shape enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3 Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.

36 MATERIALS SCIENCE↗