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At least 1,045 records · Page 58

Geochemical and mineralogical interpretation of the Viking inorganic chemical results

The current status of geochemical, mineralogical, petrological interpretation of refined Viking Lander data is reviewed, and inferences that can be drawn from data on the composition of Martian surface materials are presented. The materials are dominantly fine silicate particles admixed with, or including, iron oxide particles. Both major element and trace element abundances in all samples are indicative of mafic source rocks (rather than more highly differentiated salic materials). The surface fines are nearly identical in composition at the two widely separated Lander sites, except for some lithologic diversity at the 100-m scale. This implies that some agency (presumably aeolian processes) has thoroughly homogenized them on a planetary scale. The most plausible model for the mineralogical constitution of the fine-grained surface materials at the two Lander sites is a fine-grained mixture dominated by iron-rich smectites, or their degradation products, with ferric oxides, probably including maghemite and carbonates (such as calcite), but not such less stable phases as magnesite or siderite.

Toulmin, P., III↗

Analysis of Crystalline Defects Caused by Growth on Partially Planarized Spalled (100) GaAs Substrates

We analyze the effect of growth on non-(100) surfaces resulting from incomplete planarization of spalled GaAs wafers on the defect structure of GaAs solar cell layers grown by hydride vapor phase epitaxy (HVPE). Controlled spalling of (100)-oriented GaAs has the potential to reduce substrate costs for III-V epitaxy; however, it creates regularly faceted surfaces that may complicate the growth of high-quality III-V optoelectronic devices. We leverage the anisotropic growth rate of HVPE to planarize these faceted GaAs substrates, reducing the surface roughness and degree of faceting. We observe degraded solar cell performance and material quality in sample areas where facets are not completely removed. We used dark lock-in thermography and photoluminescence to identify recombination in areas that were not fully planarized. We used cathodoluminescence to identify the presence of extended defects in these regions, which are correlated with bandgap fluctuations in the material. We hypothesize that these defects were created by strain from compositional fluctuations in ternary alloys grown on the faceted surfaces. This work elucidates the potential issues of solar cells grown on faceted surfaces and builds understanding toward realizing high performance III-V photovoltaics with the cost-reduction potential of controlled spalling.

14 SOLAR ENERGY↗

Higher Americium Oxidation State Research Roadmap

The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non-solvent-extraction separations are also under investigation. The first would separate Am(VI) by co-crystallization with uranium and the other oxidizable actinides as their nitrate salts. This novel idea has been successful in lab scale testing, and merits further investigation. Similarly, success has been achieved in separations using inorganic or hybrid ion exchange materials to sorb the lanthanides and actinides, while allowing pentavalent americium to elute. This is the only technique currently investigating Am(V), despite the advantages of this oxidation state with regard to its higher stability. The ultimate destination for this roadmap is to develop an americium separation that can be applied under process conditions, preferably affording a co-separation of the actinyl (VI) ions. Toward that end, emphasis is given here to selection of a solvent extraction flowsheet for testing in the INL centrifugal contactor hot test bed during FY16. A solvent extraction process will be tested mainly because solvent extraction separations of Am(VI) are relatively mature and the test bed currently exists in a configuration to support them. Thus, a major goal of FY16 is to select the oxidant/ligand combination to run such a test using the contactors. The only ligands under consideration are DAAP and DEHBA. This is not to say that ion exchange and co-crystallization techniques are unimportant. They merit continued investigation, but are not mature enough for hot test bed testing at this time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cloud-Resolving ICON Simulations of Secondary Ice Production in Arctic Mixed-Phase Stratocumuli Observed during M-PACE

Field measurements and modeling studies suggest that secondary ice production (SIP) may close the gap between observed Arctic ice nucleating particle (INP) concentrations and ice crystal number concentrations ni. Here, we explore sensitivities with respect to the complexity of different INP parameterizations under the premise that ni is governed by SIP. Idealized, cloud-resolving simulations are performed for the marine cold air outbreak cloud deck sampled during the Mixed-Phase Arctic Cloud Experiment (M-PACE) with the Icosahedral Nonhydrostatic (ICON) model. The impact of the droplet shattering (DS) of raindrops and collisional breakup (BR) in addition to the existing Hallet–Mossop rime splintering mechanism were investigated. Overall, 12 different model experiments (12-h runs) were performed and analyzed. Despite the considerable amount of uncertainty remaining with regard to SIP mechanisms and their process representation in numerical models, we conclude from these experiments that (i) only simulations where DS dominates the SIP signal (potentially amplified by BR) capture observed ice-phase and liquid-phase cloud properties, and (ii) SIP events cluster around the convective outflow region and are structurally linked to mesoscale cloud organization. In addition, interactions with primary nucleation parameterizations of varied complexity were investigated. Here, our simulations show that (i) a stable long-lived mixed-phase cloud (MPC) can be maintained in the absence of primary nucleation once SIP is established, (ii) experiments using a computationally more efficient relaxation-based parameterization of primary nucleation are statistically invariant from simulations considering prognostic INP, and (iii) primary nucleation at cloud-top controls the areal extent of the mixed-phase cloud region, and reduces SIP efficacy via DS due to increased depletion of cloud liquid throughout the entire cloud column.

54 ENVIRONMENTAL SCIENCES↗

Analysis of coupled-bunch instabilities for the NSLS-II storage ring with a 500MHz 7-cell PETRA-III cavity

The NSLS-II storage ring is designed to operate with superconducting RF-cavities with the aim to store an average current of 500 mA distributed in 1080 bunches, with a gap in the uniform filling for ion clearing. At the early stage of the commissioning (phase 1), characterized by a bare lattice without damping wigglers and without Landau cavities, a normal conducting 7-cell PETRA-III RF-cavity structure has been installed with the goal to store an average current of 25 mA. In this paper we discuss our analysis of coupled-bunch instabilities driven by the Higher Order Modes (HOMs) of the 7-cell PETRA-III RF-cavity. As a cure of the instabilities, we apply a well-known scheme based on a proper detuning of the HOMs frequencies based upon cavity temperature change, and the use of the beneficial effect of the slow head–tail damping at positive chromaticity to increase the transverse coupled-bunch instability thresholds. In addition, we discuss measurements of coupled-bunch instabilities observed during the phase 1 commissioning of the NSLS-II storage ring. In our analysis we rely, in the longitudinal case, on the theory of coupled-bunch instability for uniform fillings, while in the transverse case we complement our studies with numerical simulations with OASIS, a novel parallel particle tracking code for self-consistent simulations of collective effects driven by short and long-range wakefields.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Phase transformations in oxides above 2000°C: experimental technique development

Here, the oxidation of boride and carbide-based ultra-high-temperature ceramics is the primary limiting factor for their use as aerodynamic surfaces. Understanding the behaviour of the oxides that can result from oxidation of metal borides and carbides at very high temperatures is essential to optimise and tailor the performance of these materials; yet experimental thermodynamic and structural data for refractory oxides above 2000°C are mostly absent. The following techniques that can be applied to fill this gap are discussed: (i) commercial ultra-high-temperature differential thermal analysis for investigation of phase transformations and melting in inert environments to 2500°C, (ii) a combination of laser heating with a splittable nozzle aerodynamic levitator for splat quenching and drop calorimetry from temperatures limited only by sample evaporation, (iii) synchrotron X-ray and neutron diffraction on laser-heated aerodynamically levitated oxide samples for in situ observation of phase transformations in variable atmospheres, refinement of high-temperature structures and thermal expansion. Recent experimental findings include anomalous thermal expansion of the defect fluorite phase of YSZ, thermodynamics of pyrochlore–fluorite transformation from high-temperature structure refinements, and measurement of thermal expansion to the melting temperatures and fusion enthalpies of Zr, Hf, La, Yb and Lu oxides. These methods provide temperatures, enthalpies and volume change for phase transformations above 2000°C, which are required for thermodynamic assessments and calculation of phase diagrams of multicomponent systems.

36 MATERIALS SCIENCE↗

Metal Ion Binding to the Amyloid β Monomer Studied by Native Top-Down FTICR Mass Spectrometry

Native top-down mass spectrometry is a fast, robust biophysical technique that can provide molecular-scale information on the interaction between proteins or peptides and ligands, including metal cations. Here we have analyzed complexes of the full-length amyloid β (1-42) monomer with a range of (patho)physiologically relevant metal cations using native Fourier transform ion cyclotron resonance mass spectrometry and three different fragmentation methods—collision-induced dissociation, electron capture dissociation, and infrared multiphoton dissociation—all yielding consistent results. Amyloid β is of particular interest as its oligomerization and aggregation are major events in the etiology of Alzheimer’s disease, and it is known that interactions between the peptide and bioavailable metal cations have the potential to significantly damage neurons. Those metals which exhibited the strongest binding to the peptide (Cu{sup 2+}, Co{sup 2+}, Ni{sup 2+}) all shared a very similar binding region containing two of the histidine residues near the N-terminus (His6, His13). Notably, Fe{sup 3+} bound to the peptide only when stabilized toward hydrolysis, aggregation, and precipitation by a chelating ligand, binding in the region between Ser8 and Gly25. We also identified two additional binding regions near the flexible, hydrophobic C-terminus, where other metals (Mg{sup 2+}, Ca{sup 2+}, Mn{sup 2+}, Na{sup +}, and K{sup +}) bound more weakly—one centered on Leu34, and one on Gly38. Unexpectedly, collisional activation of the complex formed between the peptide and [Co{sup III}(NH{sub 3}){sub 6}]{sup 3+} induced gas-phase reduction of the metal to Co{sup II}, allowing the peptide to fragment via radical-based dissociation pathways. This work demonstrates how native mass spectrometry can provide new insights into the interactions between amyloid β and metal cations. .

74 ATOMIC AND MOLECULAR PHYSICS↗

Advective gas flow in bentonite: Development and comparison of enhanced multi-phase numerical approaches

Understanding the impact of repository gas, generated from degradation of waste and its interaction with the host rock, is essential when assessing the performance and safety function of long-term disposal systems for radioactive waste. Numerical models based on conventional multi-phase flow theory have historically been applied to predict the outcome and impact of gas flow on different repository components. However, they remain unable to describe the full complexity of the physical processes observed in water-saturated experiments (e.g., creation of dilatant pathways) and thus, the development of novel representations for their description is required when assessing fully saturated clay-based systems. This was the primary focus of Task A within the international cooperative project DECOVALEX-2019 (D-2019) and refinement of these approaches is the primary focus of this study (Task B in the current phase of DECOVALEX-2023). This paper summarises development of enhanced numerical representations of key processes and compares the performance of each model against high-quality laboratory test data. Experimental data reveals that gas percolation in water-saturated compacted bentonite is characterised by four key features: (i) a quiescence phase, followed by (ii) the gas breakthrough, which leads to a (iii) peak value, which is then followed by (iv) a negative decay. Three models based on the multiphase flow theory have been developed. These models can provide good initial values and reasonable responses for gas breakthrough (although some of them still predict a too-smooth response). Peak gas pressure values are in general reasonably well captured, although maximum radial stress differences are observed at 48 mm from the base of the sample. Here, numerical peak values of 12.8 MPa are predicted, whereas experimental values are about 11 MPa. These models are also capable of providing a reasonable representation of the negative pressure decay following peak pressure. However, other key specific features (such as the timing of gas breakthrough) still require a better representation. The model simulations and their comparison with experimental data show that these models need to be further improved with respect to model parameter calibration, the numerical representation of spatial heterogeneities in material properties and flow localisation, and the upscaling of the related physical processes and parameters. To further understand gas flow localisation, a new conceptual model has been developed, which shows that discrete channels can possibly be induced through the instability of gas-bentonite interface during gas injection, thus providing a new perspective for modeling gas percolation in low-permeability deformable media.

58 GEOSCIENCES↗

Indium and thallium extraction into betainium bis(trifluoromethylsulfonyl)imide ionic liquid from aqueous hydrochloric acid media

The partitioning behavior of indium and thallium ions between aqueous hydrochloric acid solutions and hydrophobic betainium bis(trifluoromethylsulfonyl)imide ionic liquid was studied using a standard liquid–liquid extraction technique. The experiments were mainly carried out by means of a radiochemical method, using 111 In and 201 Tl medical radionuclides at an ultra-trace concentration. Both mono- and trivalent thallium were utilized and the highest oxidation state (3+) was produced by adding either chlorine or bromine water to the aqueous phase prior to extraction. The metal ion transfer was optimized by varying the aqueous concentration of hydrochloric acid and by introducing zwitterionic betaine as an extracting agent into the aqueous phase. It was found that the highest D values of In(III), Tl(III) and Tl(I) in the investigated chemical systems were up to 200, 70, and 1, respectively. The influence of the addition of lithium salt, having common with the ionic liquid counterion, and the variation of mixing time on the distribution ratio of the metal ions were also studied. Finally, to understand the underlying extraction mechanism of the metal ions and to propose the predominant extracted species, mathematical models based on ion pair formation and ion exchange were developed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CHAOS I. Direct chemical abundances for H II regions in NGC 628

The CHemical Abundances of Spirals (CHAOS) project leverages the combined power of the Large Binocular Telescope (LBT) with the broad spectral range and sensitivity of the Multi Object Double Spectrograph (MODS) to measure “direct” abundances (based on observations of the temperature-sensitive auroral lines) in large samples of H ii regions in spiral galaxies. We present LBT MODS observations of 62 H ii regions in the nearby spiral galaxy NGC 628, with an unprecedentedly large number of auroral lines measurements (18 [O iii] λ4363, 29 [N ii] λ5755, 40 [S iii]λ6312, and 40 [O ii] λλ7320, 7330 detections) in 45 H ii regions. Comparing derived temperatures from multiple auroral line measurements, we find: (1) a strong correlation between temperatures based on [S iii] λ6312 and [N ii] λ5755; and (2) large discrepancies for some temperatures based on [O ii] λλ7320, 7330 and [O iii] λ4363. Both of these trends are consistent with other observations in the literature, yet, given the widespread use and acceptance of [O iii] λ4363 as a temperature determinant, the magnitude of the T[O iii] discrepancies still came as a surprise. Based on these results, we conduct a uniform abundance analysis prioritizing the temperatures derived from [S iii] λ6312 and [N ii] λ5755, and report the gas-phase abundance gradients for NGC 628. Relative abundances of S/O, Ne/O, and Ar/O are constant across the galaxy, consistent with no systematic change in the upper IMF over the sampled range in metallicity. These alpha-element ratios, along with N/O, all show small dispersions (σ ∼ 0.1 dex) over 70% of the azimuthally averaged radius. We interpret these results as an indication that, at a given radius, the interstellar medium in NGC 628 is chemically well-mixed. Unlike the gradients in the nearly temperature-independent relative abundances, O/H abundances have a larger intrinsic dispersion of ∼0.165 dex. We posit that this dispersion represents an upper limit to the true dispersion in O/H at a given radius and that some of that dispersion is due to systematic uncertainties arising from temperature measurements.

79 ASTRONOMY AND ASTROPHYSICS↗

Hot and dense homogeneous nucleonic matter constrained by observations, experiment, and theory

We propose a new class of phenomenological equations of state for homogeneous matter for use in simulations of hot and dense matter in local thermodynamic equilibrium. We construct a functional form which respects experimental, observational, and theoretical constraints on the nature of matter in various density and temperature regimes. Our equation of state (EOS) matches (i) the virial coefficients expected from nucleon-nucleon scattering phase shifts, (ii) experimental measurements of nuclear masses and charge radii, (iii) observations of neutron star radii, (iv) theory results on the equation of state of neutron matter near the saturation density, and (v) theory results on the evolution of the EOS at finite temperatures near the saturation density. Our analytical model allows one to compute the variation in the thermodynamic quantities based on the uncertainties in the nature of the nucleon-nucleon interaction. Lastly, we perform a correction to ensure the equation of state is causal at all densities, temperatures, and electron fractions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Formation of Zeolites Responsible for Waste Glass Rate Acceleration: An Experimental and Computational Study for Understanding Thermodynamic and Kinetic Processes

Before nuclear waste glasses can be disposed at geological disposal facilities, a performance assessment (PA) must be conducted to provide confidence to the regulators and public that the release rates of radioisotopes and hazardous materials into the environment are below the regulatory limits. Because the release rate of radionuclides is directly related to the dissolution rate of the radionuclide-containing glass, the corrosion behavior of the glass must be well understood for the disposal site lifetime. For simplicity, glass dissolution in static conditions has been categorized into three different stages, referred to as initial rate (Stage I), residual rate (Stage II) and, depending upon the secondary phases formed, a possible delayed resumption in the alteration rate (Stage III). The last of these stages is the least understood and has the possibility to drive radionuclide release rates above regulatory thresholds.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

QUASAR HOST GALAXIES AND THE M{sub SMBH}–σ{sub *} RELATION

We analyze the emission line profiles detected in deep optical spectra of quasars to derive the mass of their super-massive black holes (SMBH) following the single-epoch virial method. Our sample consists in six radio-loud (RL) quasars and four radio-quiet (RQ) quasars. We carefully fit a broad and narrow Gaussian component for each emission line in both the Hβ (10 objects) and Hα regions (5 objects). A very good agreement of the derived SMBH masses, M{sub SMBH}, is found using the fitted broad Hβ and Hα emission lines. We compare our M{sub SMBH} results with those found by previous studies. We study the relationship between the M{sub SMBH} of the quasar and the stellar velocity dispersion, σ{sub ∗}, of the host galaxy. We use the measured M{sub SMBH} and σ{sub ∗} to investigate the M{sub SMBH}–σ{sub ∗} relation for both the RL and radio-quiet subsamples. Besides the scatter, we find a good agreement between radio-quiet quasars and AGN+quiescent galaxies and between RL quasars and AGN. Our analysis does not support the hypothesis of using σ([O iii] λ5007) as a surrogate for stellar velocity dispersions in high-mass, high-luminosity quasars. We also investigate the relationship between the 5 GHz radio-continuum luminosity, L{sub 5GHz}, of the quasar host galaxy with both M{sub SMBH} and σ{sub ∗}. We do not find any correlation between L{sub 5GHz} and M{sub SMBH}, although we observe a trend that galaxies with larger stellar velocity dispersions have larger L{sub 5GHz}. Using the results of our fitting for the narrow emission lines of [O iii] λ5007 and [N ii] λ6583 we estimate the gas-phase oxygen abundance of six quasars, being sub-solar in all cases.

79 ASTRONOMY AND ASTROPHYSICS↗

Modeling Anaerobic Soil Organic Carbon Decomposition in Arctic Polygon Tundra: Insights into Soil Geochemical Influences on Carbon Mineralization: Modeling Archive

This anaerobic carbon decomposition model framework was developed with explicit representation of fermentation, methanogenesis and iron reduction by combining three well-known modeling approaches developed in different disciplines. A pool-based model to represent upstream carbon transformations and replenishment of dissolved organic carbon (DOC) pool, a thermodynamically-based model to calculate rate kinetics and biomass growth for methanogenesis and Fe(III) reduction, and a humic ion-binding model for aqueous phase speciation and pH calculations. The combined models are implemented in the open source geochemical model PHREEQC (V3.0). Installation of PHREEQC is required to run this model. This dataset contains one zipped file and one pdf.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Spatial variation of the 3.29 and 3.40 micron emission bands within reflection nebulae and the photochemical evolution of methylated polycyclic aromatic hydrocarbons

Spectra of 3 micrometers emission features have been obtained at several positions within the reflection nebulae NGC 1333 SVS3 and NGC 2023. Strong variations of the relative intensities of the 3.29 micrometers feature and its most prominent satellite band at 3.40 micrometers are found. It is shown that (i) the 3.40 micrometers band is too intense with respect to the 3.29 micrometers band at certain positions to arise from hot band emission alone, (ii) the 3.40 micrometers band can be reasonably well matched by new laboratory spectra of gas-phase polycyclic aromatic hydrocarbons (PAHs) with alkyl (-CH3) side groups, and (iii) the variations in the 3.40 micrometers to 3.29 micrometers band intensity ratios are consistent with the photochemical erosion of alkylated PAHs. We conclude that the 3.40 micrometers emission feature is attributable to -CH3 side groups on PAH molecules. We predict a value of 0.5 for the peak intensity ratio of the 3.40 and 3.29 micrometers emission bands from free PAHs in the diffuse interstellar medium, which would correspond to a proportion of one methyl group for four peripheral hydrogens. We also compare the 3 micrometers spectrum of the proto-planetary nebula IRAS 05341+0852 with the spectrum of the planetary nebula IRAS 21282+5050. We suggest that a photochemical evolution of the initial aliphatic and aromatic hydrocarbon mixture formed in the outflow is responsible for the changes observed in the 3 micrometers emission spectra of these objects.

NASA Center ARC↗