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At least 1,549 records · Page 86

Ambient vapor sampling and selective cluster formation for the trace detection of tributyl phosphate via atmospheric flow tube mass spectrometry

In addition to serving as an f-element ligand and rare-earth method complexing agent, tributyl phosphate (TBP) is a compound containing core functional groups that mimic those routinely found in degradation products from industrial processes. Because detection of trace quantities of TBP can provide insight into the routes of contamination and degradation in the environment, there is a need to develop methods capable of detecting trace quantities of TBP. Vapor detection at atmospheric pressure is one approach that is both sensitive and rapid. We present here the use of atmospheric flow tube mass spectrometry (AFT-MS) for the ambient vapor sampling of TBP from headspace of ppb-level solutions in methanol. Gas phase clustering reactions were to enhance detection levels via the addition of small quantities of the dopants diethylamine (DEA), triethylamine (TEA), and pinacolyl methylphosphonate (PMP) in the vapor stream. Detection of the TBP vapor emanating from these solutions demonstrated a linear range for the protonated TBP species of 1-1000 ppb from solution. The clusters of TBP with DEA, TEA, and PMP each yielded linear ranges of 1-250 ppb for TBP in solution. Despite smaller linear ranges, the addition of these dopant species added a layer of analytical selectivity and reduced variability in signals from quality control samples. These data were obtained using an AFT source coupled to a linear ion trap mass spectrometer, which demonstrates the applicability of trapping systems to the AFT ionization technique while monitoring positive ions.

Ambient vapor sampling, Dielectric barrier dischar↗

Year-round trace gas measurements in the central Arctic during the MOSAiC expedition

Despite the key role of the Arctic in the global Earth system, year-round in-situ atmospheric composition observations within the Arctic are sparse and mostly rely on measurements at ground-based coastal stations. Measurements of a suite of in-situ trace gases were performed in the central Arctic during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition. These observations give a comprehensive picture of year-round near-surface atmospheric abundances of key greenhouse and trace gases, i.e., carbon dioxide, methane, nitrous oxide, ozone, carbon monoxide, dimethylsulfide, sulfur dioxide, elemental mercury, and selected volatile organic compounds (VOCs). Redundancy in certain measurements supported continuity and permitted cross-evaluation and validation of the data. This paper gives an overview of the trace gas measurements conducted during MOSAiC and highlights the high quality of the monitoring activities. In addition, in the case of redundant measurements, merged datasets are provided and recommended for further use by the scientific community.

54 ENVIRONMENTAL SCIENCES↗

Species- and element-specific patterns of metal flux from contaminated wetlands versus metals shed with exuviae in emerging dragonflies

Dragonfly adults and their aquatic immature stages are important parts of food webs and provide a link between aquatic and terrestrial components. During emergence, contaminants can be exported into terrestrial food webs as immature adults fly away or be shed with their exuviae and remain in the wetland. Our previous work established metals accumulating in dragonfly nymphs throughout a contaminated constructed wetland designed to regulate pH and sequester trace metals from an industrial effluent line. In this paper we evaluated the concentration and mass of metals leaving the wetland in flying emergents versus remaining in the wetland with the shed exuviae in 10 species of dragonflies belonging to 8 genera. Nine elements (Cu, Zn, Cd, Mn, V, Mg, Fe, Al, Pb) were evaluated that include essential and nonessential elements as well as trace and major metals. Metal concentrations in the emergent body and exuviae can differ by orders of magnitude. Aluminum, Fe, Mn, and Pb were largely shed in the exuviae. Vanadium and Cd were more variable among species but also tended to be shed with the exuviae. In contrast, Cu, Zn, and Mg showed a higher tendency to leave the wetland with an emerging dragonfly. Metals shed in dragonfly exuviae can moderate the transport of metals from contaminated wetlands. Taxonomic- and metal-specific variability in daily metal flux from the wetland depended upon concentration accumulated, individual body mass, and number of individuals emerging, with each factor's relative importance often differing among species. This illustrates the importance of evaluating the mass of metals in an individual and not only concentrations. Furthermore, differences in numbers of each species emerging will magnify differences in individual metal flux when calculating community metal flux. A better understanding of the variability of metal accumulation in nymphs/larvae and metal shedding during metamorphosis among both metals and species is needed.

54 ENVIRONMENTAL SCIENCES↗

System and method for focal-plane angular-spatial illuminator/detector (fasid) design for improved graded index lenses

The present disclosure relates to a method for imaging an optical signal received by a graded index (GRIN) optical element to account for known variations in a graded index distribution of the GRIN optical element. The method may involve using a plurality of optical detector elements to receive optical rays received by the GRIN optical element at a plane, where the plane forms a part of the GRIN optical element or is downstream of the GRIN optical element relative to a direction of propagation of the optical rays. The optical rays are then traced to a plurality of additional specific locations on the plane based on the known variations in the graded index distribution of the GRIN optical element. A processor may be used to determine information on both an intensity and an angle of the received optical rays at each one of the plurality of specific locations on the plane of the GRIN optical element.

Feigenbaum, Eyal↗

Microstructure development and properties of micro-alloyed copper, Cu-0.3Zr-0.15Ag, produced by electron beam additive manufacturing

A micro-alloyed copper powder, Cu-0.3Zr-0.15Ag wt.%, was produced using gas atomization reaction synthesis. Zirconium was added to copper to sequester the oxygen present as copper oxide surface films on the powder particles. The as-received powders, as well as the intentionally oxidized powders were used to fabricate solid test articles by electron beam powder bed fusion additive manufacturing. Dense samples fabricated from as-received powder demonstrated nominal UTS, yield, and elongation values at 260 MPa, 150 MPa, and 34%, respectively. The average electrical conductivity of these samples was measured at 95% of the international annealed copper standard (IACS). Samples fabricated from the oxidized powder exhibited nominal UTS, yield, and elongation of 241 MPa, 146 MPa, and 43%, respectively, with an electrical conductivity of 95 % IACS. During characterization, it was observed that, rather than forming nano-scale dispersoids, the Zirconia (ZrO 2 ) appeared as discontinuous stringers in the metallographic cross-sections that crossed grain and melt pool boundaries. This was rationalized by tracing the presence of the micro-alloying addition of elemental zirconium, which was found to react with surface oxides dissociated in the melt pool to form ZrO 2 , which then solidified on the surface of the melt pool through an allotropic transformation to monoclinic ZrO 2 in discontinuous films and spheroids ranging in size from nanometers to microns. This was confirmed by microscopic analysis of the tops of the melt pools. On subsequent melt passes, these ZrO 2 structures were displaced and redistributed within the melt pool.

36 MATERIALS SCIENCE↗

Predominant Proton Insertion during Electrochemical Cycling of ε-VOPO 4 in a Nonaqueous Ca-Ion Electrolyte

Calcium-ion batteries (CIBs) are promising for next-generation energy storage systems. However, many reported Ca-ion storage mechanisms lack direct structural evidence, raising concerns that the observed electrochemistry may instead originate from proton insertion. Herein, we investigate the electrochemical cycling of a VOPO 4 electrode in an aprotic Ca electrolyte with trace water to clarify the charge storage mechanism. While electrochemistry, elemental analysis, and X-ray absorption spectroscopy seem to support Ca-ion intercalation in the VOPO 4 electrode, X-ray diffraction and electron microscopy unequivocally show proton insertion as the predominant charge storage mechanism. The apparent variation of Ca content in the electrode with the state of charge is attributed to the formation and dissolution of Ca-containing precipitates on the surface of VOPO 4 particles. Our work demonstrates the propensity of proton participation in the intercalation reaction in Ca-ion batteries and the necessity of structural evidence in understanding reactions in multivalent electrochemical systems.

Wang, Jiwei [Binghamton University, NY (United Sta↗

Bubble Formation on a Wall in Cross-Flowing Liquid and Surrounding Fluid Motion,With and Without Heating

Application of gas-liquid two-phase flow systems for space-based thermal management and for the HEDS program demands a precise control of bubble size distribution in liquid. The necessity of bulk liquid motion for controlling bubble size and frequency in the space environment has been suggested by recent studies on pool, forced convection boiling and bubble formation in flowing liquid. The present work, consisting of two parts, explores bubble generation at wall in a cross-flowing liquid, i.e., in a forced convection boiling configuration. A schematic is shown. The first part looks into the bubble formation process under isothermal conditions in a reduced gravity environment, by injecting gas through a hole in the wall of a flowing liquid channel. In the latter part with channel wall heating, flow and temperature fields near a single bubble are studied under normal (1-g) and micro-gravity (mu-g) conditions. The objective of the isothermal experiments is to experimentally investigate the effects of liquid cross-flow velocity, gas flow rate, and orifice diameter on bubble formation. Data were taken mainly under reduced gravity conditions but some data were taken in normal gravity for comparison. The reduced gravity experiment was conducted aboard the NASA DC-9 Reduced Gravity Aircraft. The results show that the process of bubble formation and detachment depends on gravity, the orifice diameter (D(sub N)), the gas flow rate (Q(sub g)), and the liquid cross-flow velocity (U(sub L)). The reduced gravity data are shown. The data are analyzed based on a force balance, and two different detachment mechanisms are identified. When the gas momentum is large, the bubble detaches from the injection orifice as the gas momentum overcomes the attaching effects of liquid drag and inertia. The surface tension force is much reduced because a large part of the bubble pinning edge at the orifice is lost as the bubble axis is tilted by the liquid flow. When the gas momentum is small, the force balance in the liquid flow direction is important, and the bubble detaches when the bubble axis inclination exceeds a certain angle. With wall heating, liquid motion around an air bubble in cross-flowing 2cs silicone oil is experimentally investigated in 1-g. A spectral element based steady 2D numerical model is also developed. The traces of particles from experimental flow visualization and the corresponding computed streamlines are shown. At the upstream side of the bubble facing the cross-flow, thermocapillary and forced convection create liquid motion away from the wall, up along the surface. At the downstream side, a competing interaction between the two creates a recirculation cell, causing the bulk liquid to stagnate on the surface and separate thereafter. The important dimensionless parameters are - Surface tension and local cross-flow Reynolds numbers R(sub sigma)(U(sub ref)a/v) and Re(sub loc)(U(sub L)a/v), respectively based on reference thermocapillary U(sub ref)(sigma(sub T)Delta.T/mu, Delta T=T(sub wall)-T(sub liquid)) and local cross-flow velocity U(sub L), Prandtl number P(sub r) and Grashoff number Gr(rho.g.beta.DeltaTa(sup 3)/mu.v). Variation of the stagnation point with R(sub sigma) and Re(sub loc) is shown. Also shown are good agreement between experimental and numerical results in 1-g. The computational model is extended to mu-g condition to investigate temperature and velocity on the bubble surface, stagnation and reattachment points of the recirculation cell and wall heat transfer. It is observed that wall heating significantly alters the flow field around the bubble and thus the forces acting on the bubble, which control its detachment. Thus a combination of heating and liquid cross-flow can be utilized to precisely control bubble formation in a mu-g environment.

Bhunia, Avijit↗

Integrated Modeling of Optical Systems (IMOS): An Assessment and Future Directions

Integrated Modeling of Optical Systems (IMOS) is a finite element-based code combining structural, thermal, and optical ray-tracing capabilities in a single environment for analysis of space-based optical systems. We'll present some recent examples of IMOS usage and discuss future development directions. Due to increasing model sizes and a greater emphasis on multidisciplinary analysis and design, much of the anticipated future work will be in the areas of improved architecture, numerics, and overall performance and analysis integration.

Moore, Gregory↗

Validation and uncertainty of DRF's for a 1"×2" NaI collimated detector for radioisotope holdup measurements

Detector response functions (DRFs) have become the subject of increasing scientific interest for the last thirty years in several industrial applications of radiation detection. These applications include gamma-ray, prompt gamma-ray, and X-ray spectrometry for elemental analysis and location as applied to mining, radio-tracing in medicine, and holdup source characterization. However, it is difficult to create a rigorous mathematical formulation of the DRF. Therefore, semi-empirical and stochastic approaches have been developed instead to construct detector and application specific DRFs. A DRF can be considered to be a function that converts the energy-dependent incidence of incoming source particles onto a detector into a detector response spectrum that simulates the experimental response. The DRF can also be used in the reverse sense in an inverse problem setting, as a step in the process of predicting the physical characteristics of an unknown source (e.g. the holdup problem and library spectra). Much of the recent work on DRFs has been performed by Gardner. He has developed accurate DRF models through semi-empirical curve fitting and Monte Carlo simulation. His DRFs for 3" X 3" NaI detectors have been developed with the experimental measurements taken by Heath and for 6"x6" bare (unshielded) NaI(Tl) detector data with single-energy sources centered on the detector face at a distance of 10 cm. There was agreement with the Heath benchmark detector measurements within two Poisson standard deviations of the measured data. DRFs have also been developed for other detectors such as high purity Germanium detectors and Si(Li) for the same geometries as NaI. Other than a few artifacts such as backscatter peaks, there was good agreement between simulated responses and the experimental data.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Future chlorine-bromine loading and ozone depletion

The prediction of future ozone requires three elements: (1) a scenario for the net emissions of chemically and radiatively active trace gases from the land and oceans; (2) a global atmospheric model that projects the accumulation of these gases; and (3) a chemical transport model that describes the distribution of ozone for a prescribed atmospheric composition and climate. This chapter, of necessity, presents models for all three elements and focuses on the following: (1) atmospheric abundance of chlorine and bromine in the form of halocarbons; and (2) the associated perturbations to stratospheric ozone.

Prather, Michael J.↗

The Relationship between Age, Metallicity, and Abundances for Disk Stars in a Simulated Milky Way

Observations of the Milky Way's low-α disk show that several element abundances correlate with age at fixed metallicity, with unique slopes and small scatters around the age–[X/Fe] relations. In this study, we turn to simulations to explore the age–[X/Fe] relations for the elements C, N, O, Mg, Si, S, and Ca that are traced in a FIRE-2 cosmological zoom-in simulation of a Milky Way–like galaxy, m12i, and understand what physical conditions give rise to the observed age–[X/Fe] trends. We first explore the distributions of mono-age populations in their birth and current locations, [Fe/H], and [X/Fe], and find evidence for inside-out radial growth for stars with ages <7 Gyr. We then examine the age–[X/Fe] relations across m12i's disk and find that the direction of the trends agrees with observations, apart from C, O, and Ca, with remarkably small intrinsic scatters, σ int (0.01 - 0.04 dex). This σ int measured in the simulations is also metallicity dependent, with σ int ≈ 0.025 dex at [Fe/H] = -0.25 dex versus σ int ≈ 0.015 dex at [Fe/H] = 0 dex, and a similar metallicity dependence is seen in the GALAH survey for the elements in common. Additionally, we find that σ int is higher in the inner galaxy, where stars are older and formed in less chemically homogeneous environments. The age–[X/Fe] relations and the small scatter around them indicate that simulations capture similar chemical enrichment variance as observed in the Milky Way, arising from stars sharing similar element abundances at a given birth place and time.

79 ASTRONOMY AND ASTROPHYSICS↗

Uncollided-Flux Treatment for Discrete-Ordinate Radiation Transport Solutions in the Rattlesnake Code System

We present the uncollided-flux treatment implemented in the Rattlesnake code system of the Idaho National Laboratory (INL). The ray-tracing method employed is capable of handling various types of finite-element meshes. Uncollided-flux techniques are necessary to capture streaming in low-density regions, such as the ones found in the TREAT test reactor at INL. Numerical results are presented.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Mars Solar Balloon Landed Gas Chromatograph Mass Spectrometer

A Mars surface lander Gas Chromatograph Mass Spectrometer (GCMS) is described to measure the chemical composition of abundant and trace volatile species and isotope ratios for noble gases and other elements. These measurements are relevant to the study of atmospheric evolution and past climatic conditions. A Micromission plan is under study where a surface package including a miniaturized GCMS would be delivered to the surface by a solar heated hot air balloon based system. The balloon system would be deployed about 8 km above the surface of Mars, wherein it would rapidly fill with Martian atmosphere and be heated quickly by the sun. The combined buoyancy and parachuting effects of the solar balloon result in a surface package impact of about 5 m/sec. After delivery of the package to the surface, the balloon would ascend to about 4 km altitude, with imaging and magnetometry data being taken for the remainder of the daylight hours as the balloon is blown with the Martian winds. Total atmospheric entry mass of this mission is estimated to be approximately 50 kg, and it can fit as an Ariane 5 piggyback payload. The GCMS would obtain samples directly from the atmosphere at the surface and also from gases evolved from solid phase material collected from well below the surface with a Sample Acquisition and Transport Mechanism (SATM). The experiment envisioned in the Mars Micromission described would obtain samples from a much greater depth of up to one meter below the surface, and would search for organic molecules trapped in ancient stratified layers well below the oxidized surface. Insitu instruments on upcoming NASA missions working in concert with remote sensing measurement techniques have the potential to provide a more detailed investigation of mineralogy and the extent of simple volatiles such as CO2 and H2O in surface and subsurface solid phase materials. Within the context of subsequent mission opportunities such as those provided by the Ariane 5 piggyback payload based Micromissions, it is essential to implement an even broader chemical analysis and to enable a significant extension of previous isotope measurements. Such a development would enhance the presently very active study of questions of atmospheric evolution and loss and past climatic conditions. The method selected to implement this program can be based on well-established mass spectrometry techniques. Sampled gas is chemically and physically processed to separate the gas mixture into components using gas chromatograph and related enrichment techniques. This allows trace species to be identified and reveals isotopic distributions in many cases with improved precision. Samples of interest, such as organic molecules, may lie deep below the highly oxidized surface layer and the suggested program includes enhanced sampling techniques to measure volatiles preserved in solid phase material deep below the surface as well as gas from the well mixed atmosphere.

Mahaffy, P.↗

Implementation of a Novel Low-Cost Low-Profile Ku-Band Antenna Array for Single Beam Steering from Space

Phased array antennas afford many advantages over traditional reflector antennas due to their conformality, high aperture efficiency, and unfettered beam steering capability at the price of increased cost and complexity. This paper eliminates the complex and costly array backend via the implementation of a series fed array employing a propagation constant reconfigurable transmission line connecting each element in series. Scanning can then be accomplished through one small (less than or equal to 100mil) linear motion that controls propagation constant. Specifically, each element is fed via a reconfigurable coplanar stripline transmission line with a tapered dielectric insert positioned between the transmission line traces. The dielectric insert is allowed to move up and down to control propagation constant and therefore induce scanning. We present a 20 element patch array design, scanning from -25 deg. less than or equal to theta less than or equal to 21 deg. at 13GHz. Measurements achieve only10.5 deg. less than or equal to theta less than or equal to 22 deg. scanning due to a faulty, yet correctable, manufacturing process. Beam squint is measured to be plus or minus 3 deg. for a 600MHz bandwidth. This prototype was improved to give scanning of 3.5 deg. less than or equal to theta less than or equal to 22 deg. Cross-pol patterns were shown to be -15dB below the main beam. Simulations accounting for fabrication errors match measured patterns, thus validating the designs.

Reconfigurable Transmission Lines↗

Are the Formation and Abundances of Metal-poor Stars the Result of Dust Dynamics?

Large dust grains can fluctuate dramatically in their local density, relative to the gas, in neutral turbulent disks. Small, high-redshift galaxies (before reionization) represent ideal environments for this process. We show via simple arguments and simulations that order-of-magnitude fluctuations are expected in local abundances of large grains (>100 Å) under these conditions. This can have important consequences for star formation and stellar metal abundances in extremely metal-poor stars. Low-mass stars can form in dust-enhanced regions almost immediately after some dust forms even if the galaxy-average metallicity is too low for fragmentation to occur. We argue that the metal abundances of these “promoted” stars may contain interesting signatures as the CNO abundances (concentrated in large carbonaceous grains and ices) and Mg and Si (in large silicate grains) can be enhanced and/or fluctuate almost independently. Remarkably, the otherwise puzzling abundance patterns of some metal-poor stars can be well fit by standard IMF-averaged core-collapse SNe yields if we allow for fluctuating local dust-to-gas ratios. We also show that the observed log-normal distribution of enhancements in pure SNe yields, shows very large enhancements and variations up to factors of ≳100 as expected in the dust-promoted model, preferentially in the [C/Fe]-enhanced metal-poor stars. Together, this suggests that (1) dust exists in second-generation star formation, (2) local dust-to-gas ratio fluctuations occur in protogalaxies and can be important for star formation, and (3) the light element abundances of these stars may be affected by the local chemistry of dust where they formed, rather than directly tracing nucleosynthesis from earlier populations.

79 ASTRONOMY AND ASTROPHYSICS↗

A survey of the core-congruential formulation for geometrically nonlinear TL finite elements

This article presents a survey of the core-congruential formulation (CCF) for geometrically nonlinear mechanical finite elements based on the total Lagrangian (TL) kinematic description. Although the key ideas behind the CCF can be traced back to Rajasekaran and Murray in 1973, it has not subsequently received serious attention. The CCF is distinguished by a two-phase development of the finite element stiffness equations. The initial phase developed equations for individual particles. These equations are expressed in terms of displacement gradients as degrees of freedom. The second phase involves congruential-type transformations that eventually binds the element particles of an individual element in terms of its node-displacement degrees of freedom. Two versions of the CCF, labeled direct and generalized, are distinguished. The direct CCF (DCCF) is first described in general form and then applied to the derivation of geometrically nonlinear bar, and plane stress elements using the Green-Lagrange strain measure. The more complex generalized CCF (GCCF) is described and applied to the derivation of 2D and 3D Timoshenko beam elements. Several advantages of the CCF, notably the physically clean separation of material and geometric stiffnesses, and its independence with respect to the ultimate choice of shape functions and element degrees of freedom, are noted. Application examples involving very large motions solved with the 3D beam element display the range of applicability of this formulation, which transcends the kinematic limitations commonly attributed to the TL description.

Felippa, Carlos A.↗

Oxidation of manganese in an ancient aquifer, Kimberley formation, Gale crater, Mars

We report that the Curiosity rover observed high Mn abundances (>25 wt % MnO) in fracture-filling materials that crosscut sandstones in the Kimberley region of Gale crater, Mars. The correlation between Mn and trace metal abundances plus the lack of correlation between Mn and elements such as S, Cl, and C, reveals that these deposits are Mn oxides rather than evaporites or other salts. On Earth, environments that concentrate Mn and deposit Mn minerals require water and highly oxidizing conditions; hence, these findings suggest that similar processes occurred on Mars. In conclusion, based on the strong association between Mn-oxide deposition and evolving atmospheric dioxygen levels on Earth, the presence of these Mn phases on Mars suggests that there was more abundant molecular oxygen within the atmosphere and some groundwaters of ancient Mars than in the present day.

36 MATERIALS SCIENCE↗

Improve the efficiency of the Cartesian tensor based fast multipole method for Coulomb interaction using the traces

To compute the non-oscillating mutual interaction for a systems with N points, the fast multipole method (FMM) has an efficiency that scales linearly with the number of points. Specifically, for Coulomb interaction, FMM can be constructed using either the spherical harmonic functions or the totally symmetric Cartesian tensors. In this paper, we will present that the effciency of the Cartesian tensor-based FMM for the Coulomb interaction can be significantly improved by implementing the traces of the Cartesian tensors in calculation to reduce the independent elements of the n-th rank totally symmetric Cartesian tensor from (n + 1)(n + 2)=2 to 2n + 1. The computation complexity for the operations in FMM are analyzed and expressed as polynomials of the highest rank of the Cartesian tensors. For most operations, the complexity is reduced by one order. Numerical examples regarding the convergence and the effciency of the new algorithm are demonstrated. As a result, a reduction of computation time up to 50% has been observed for a moderate number of points and rank of tensors.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗