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At least 577 records · Page 32

Probing Heterogeneity in Bovine Enamel Composition through Nanoscale Chemical Imaging using Atom Probe Tomography

Objective: The aim of this study was to determine the heterogeneity in chemical composition of bovine enamel using atom probe tomography, and thereby evaluate the suitability of bovine enamel as a substitute for human enamel in in vitro dental research. Design: Enamel samples from extracted bovine incisor teeth were first sectioned using a diamond saw and then milled into needle-like samples (<100 nm diameter) by focused ion beam (FIB) coupled with a scanning electron microscope (SEM). The samples were then analyzed in the atom probe to acquire three-dimensional (3D) images and quantify the atomic chemistry and distribution in bovine enamel. Results: For the first time, the atomic-level composition and clustering of major constituents and impurities within bovine enamel were determined and imaged. We discovered that the chemical composition of bovine enamel is spatially inhomogeneous at the atomic scale. The average bulk Ca/P ratio, ~1.4, was in agreement with previously reported literature values from alternative conventional methods. When assessed locally at the atomic scale, the Ca/P ratio varied between 1.1 and 2.03. We also discovered that the Mg impurities were significantly segregated throughout the enamel, and such clustering influenced the variation of Ca/P ratios. The increase in Mg concentrations, near the Mg clusters, correlated with increased Ca and decreased P concentrations. Conclusion: In conclusion, the presented findings of variability in local composition should be taken into account when interpreting dental research results from bovine enamel.

59 BASIC BIOLOGICAL SCIENCES↗

Vacuum-ultraviolet absorption cross-sections of functionalized cyclic hydrocarbons: Five-membered rings

Cross-sections were measured at 50 °C and 800 Torr using differential absorption spectroscopy in the vacuum-ultraviolet from 5.17 – 9.92 eV for a series of five-membered cyclic hydrocarbons: cyclopentane, cyclopentene, methylcyclopentane, tetrahydrofuran, furan, 2-methyltetrahydrofuran, 2,3-dihydro-5-methylfuran, tetrahydrofuran-3-one, 2-methyl-1,3-dioxolane, cyclopentanol, 2-hydroxytetrahydrofuran, cyclopentanone, 2-cyclopenten-1-one, 3-cyclopenten-1-one, 2-methylcyclopentan-1-one, 2-methylcyclopent-2-en-1-one, 1,2-epoxycyclopentane, 2,3-epoxycyclopentanone, and 3,4-epoxycyclopentanone. The majority of the species are functionalized and are directly related to chain-reactions relevant to combustion, such as substituted cyclic ethers and cycloalkenes. Uncertainty calculations were conducted as a function of photon energy to quantify errors associated with experimental repeatability, signal-to-noise ratio, and gas-phase concentration, yielding an upper limit of 5% in spectral regions where absorption is >2%. Here, the primary objective of the present work is to provide quantitative absorption cross-sections of species commonly produced in combustion reactions. Comparing qualitative differences among the five-membered cyclic species, in order to analyze the effect of functional groups on absorption, is a secondary objective. The majority of the spectra are reported for the first time and enable quantitative isomer-resolved speciation measurements in combustion chemistry.

74 ATOMIC AND MOLECULAR PHYSICS↗

Molecular-level insights into structure and dynamics in ionic liquids and polymer gel electrolytes

We report designing new electrolytes requires a better understanding of the correlation between their transport properties and their molecular structure. In this work, we present a detailed study of ionic liquids and polymer gel electrolytes probing their structure and dynamics by nuclear magnetic resonance (NMR) spectroscopy. In particular, ammonium- and phosphonium-based ionic liquids (ILs) are combined with different LiTFSI concentrations, and then with different ratios of poly(methylmethacrylate) polymer. The temperature dependence of self-diffusion coefficients of mobile species, D Li+ , D TFSI- and D P4441+ or D N4441+ , measured by pulsed field gradient (PFG) NMR spectroscopy obeys the Arrhenius equation. Diffusivity of [P4441][TFSI] ILs is found to be greater than those of the [N4441][TFSI] ILs in both liquid and gel electrolytes. Solid state NMR experiments including 13 C and 19 F MAS, 13 C{ 19 F}, 13 C{ 1 H} CPMAS probe the local structure and molecular-level interactions between ions and polymer in gel electrolytes, particularly for samples with higher PMMA content (≥25 wt%). Finally, the fast field cycling relaxometry has been used to unveil the rotational and translational dynamics of P4441 + or N4441 + and TFSI - by measuring 1 H and 19 F R 1 relaxation rate profiles at different temperatures. A comprehensive NMR analysis including relaxation studies at low magnetic field provides decisive new insights regarding the formation of ionic clusters and the interaction of ions with the polymer chain in the case of the gel electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling Ion Coordination Structure and Diffusion Kinetics for Optimized Electrode-Electrolyte Interphases and High Performance Si Anodes

The cycling performance of batteries is largely determined by electrode-electrolyte interphase associated with the chemical and electrochemical properties of electrolyte salts and solvents. In this work, we used a localized high concentration electrolyte (LHCE) that enables high performance of Si anodes as a model system and investigated the scientific mechanism behind the optimization of electrolyte. The correlation between electrode (cathode/anode)-electrolyte interphase and ion coordination structure and diffusion kinetics were elucidated systematically. Among all the LHCEs tested, the one with 1.8M LiFSI concentration and 1:2 molar ratio of carbonate solvents and fluorinated diluents has the highest proportion of solvent-separated ion pairs and contact ion pairs and fastest ion diffusion. It enables the most stable electrode-electrolyte interphase and hence the best Si anode performance. These results reveal the fundamental mechanism behind the stability of LHCEs and provide guidance on the new electrolyte design for Si anodes and other battery systems.

Jia, Haiping↗

Effect of Natural Organic Matter on the Fate of Cadmium During Microbial Ferrihydrite Reduction

Natural organic matter (NOM) is known to affect the microbial reduction and transformation of ferrihydrite, but its implication toward cadmium (Cd) associated with ferrihydrite is not well-known. In this work, we investigated how Cd is redistributed when ferrihydrite undergoes microbial reduction in the presence of NOM. Incubation with Geobacter sulfurreducens showed that both the rate and the extent of reduction of Cd-loaded ferrihydrite were enhanced by increasing concentrations of NOM (i.e., C/Fe ratio). Furthermore, without NOM, only 3–4% of Fe(III) was reduced, but around 61% of preadsorbed Cd was released into solution due to ferrihydrite transformation to lepidocrocite. At high C/Fe ratio (1.6), more than 35% of Fe(III) was reduced, as NOM can facilitate bioreduction by working as an electron shuttle and decreased aggregate size, but only a negligible amount of Cd was released into solution, thus decreasing Cd toxicity and prolonging microbial Fe(III) reduction. No ferrihydrite transformation was observed at high C/Fe ratios using Mössbauer spectroscopy and X-ray diffraction, and X-ray absorption spectroscopy indicated the proportion of Cd-OM bond increased after microbial reduction. This study shows that the presence of NOM leads to less mobilization of Cd under reducing condition possibly by inhibiting ferrihydrite transformation and recapturing Cd through Cd-OM bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Environmental drivers of increased ecosystem respiration in a warming tundra

Abstract Arctic and alpine tundra ecosystems are large reservoirs of organic carbon 1,2 . Climate warming may stimulate ecosystem respiration and release carbon into the atmosphere 3,4 . The magnitude and persistency of this stimulation and the environmental mechanisms that drive its variation remain uncertain 5–7 . This hampers the accuracy of global land carbon–climate feedback projections 7,8 . Here we synthesize 136 datasets from 56 open-top chamber in situ warming experiments located at 28 arctic and alpine tundra sites which have been running for less than 1 year up to 25 years. We show that a mean rise of 1.4 °C [confidence interval (CI) 0.9–2.0 °C] in air and 0.4 °C [CI 0.2–0.7 °C] in soil temperature results in an increase in growing season ecosystem respiration by 30% [CI 22–38%] (n = 136). Our findings indicate that the stimulation of ecosystem respiration was due to increases in both plant-related and microbial respiration (n = 9) and continued for at least 25 years (n = 136). The magnitude of the warming effects on respiration was driven by variation in warming-induced changes in local soil conditions, that is, changes in total nitrogen concentration and pH and by context-dependent spatial variation in these conditions, in particular total nitrogen concentration and the carbon:nitrogen ratio. Tundra sites with stronger nitrogen limitations and sites in which warming had stimulated plant and microbial nutrient turnover seemed particularly sensitive in their respiration response to warming. The results highlight the importance of local soil conditions and warming-induced changes therein for future climatic impacts on respiration.

Science & Technology - Other Topics↗

Spatiotemporal characterization of cerium monoxide in laser ablation plasmas using spectrally-resolved fast-gated imaging

The impact of oxidation chemistry on the emission characteristics and spatial structure of laser-produced Ce metal plasmas was investigated using laser-induced breakdown spectroscopy (LIBS) and time-resolved fast-gated imaging employing narrowband optical filters. Images of the plasma emission show that CeO coexists with atomic species in the periphery and vortex ring of the plasma plume. Image processing was also applied to combine independent monochromatic images of the plasma emission into a single merged image, culminating in a timelapse on the spatiotemporal evolution of atomic and molecular species within the plasma plume. The formation of CeO species was observed to proceed faster for plasmas generated in atmospheres containing larger concentrations of oxygen based on ratios of CeO-to-atomic emission intensities. Furthermore, these same ratios were shown to plateau and decrease at later times (≥25 μs), potentially indicating the depletion of CeO number densities in the plasma as the monoxide undergoes reactions to form higher polyatomic oxides. Altogether, these results provide fundamental insights into the chemical dynamics and intermixing between plasma-gas species in laser ablation cerium plasmas, advancing our understanding on optical signatures of nuclear-relevant materials to enable in-field measurement capabilities.

47 OTHER INSTRUMENTATION↗

Investigating the large-scale environment of wide-angle tailed radio galaxies in the local Universe

We present a statistical analysis of the large-scale (up to two Mpc) environment of a homogeneous and complete sample, both in radio and optical selection, of wide-angle tailed radio galaxies (WATs) in the local Universe (i.e., with redshifts z ≲ 0.15). The analysis is carried out using the parameters obtained from cosmological neighbors within two Mpc of the target source. Results regarding the large-scale environments of the WATs are then compared with those of Fanaroff–Riley type I (FR Is) and type II (FR IIs) radio galaxies listed in two other homogeneous and complete catalogs and selected with the same criterion adopted for the WATs catalog. We obtain indication that at low redshift, WATs inhabit environments with a larger number of galaxies than those of FR Is and FR IIs. In the explored redshift range, the physical size of the galaxy group or cluster in which the WATs reside appears to be almost constant with respect to FR Is and FR IIs, being around one Mpc. From the distribution of the concentration parameter, defined as the ratio between the number of cosmological neighbors lying within 500 kpc and within one Mpc, we conclude that WATs tend to inhabit the central region of the group or cluster in which they reside, in agreement with the general paradigm that WATs are the brightest cluster or group galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗

Tuning plasma parameters to control reactive species fluxes to substrates in the context of plasma catalysis

The key reactive plasma-produced gas phase species responsible for the enhanced conversion of chemicals in plasma catalysis compared to thermal catalysis have to date not been identified. This outstanding question is mainly due to the inherent large variety of plasma-produced species and the challenge of controlling and measuring the flux of each constituent of the cocktail of reactive species to a (catalytic) substrate. In this paper, we explore the possibility to control the dominant reactive species fluxes, relevant for plasma-catalysis, to a substrate in the effluent of an RF driven Ar-O 2 plasma jet. The absolute species densities of the major reactive species (O, O 2 (a 1 Δ g ), O 3 and ions) were quantified by molecular beam mass spectrometry (MBMS) to assess the possibility of using treatment distance, O 2 admixture concentration, plasma dissipated power, RF modulation frequency and duty cycle as well as the feed gas flow rate to alter the dominant species densities. Selected experimental results were also compared with a pseudo-1D plug flow model. The short-lived and long-lived species can be effectively separated by changing the treatment distance and the RF modulation frequency. Furthermore, adjusting the O 2 admixture concentration enables to change the ratio of the O 2 (a 1 Δ g ) and O 3 density. The changes in the trend of ion and O flux were found to be very similar for nearly all investigated parameters. Nonetheless the gas flow rate was able to significantly change the ratio of the O and ion density in the plasma jet effluent. Here, the impact of the surface-dependent loss probability and boundary layer reactions on the species flux to a substrate and how this qualitatively relates to the MBMS density measurements is further addressed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Dimensionless parameters for cloudy Rayleigh-Bénard convection: Supersaturation, Damköhler, and Nusselt numbers

In steady-state Rayleigh-Bénard convection, heat is transported by turbulent thermal convection from the bottom, hot surface to the top, cold surface, leading to a height-independent sensible heat flux. When water vapor is present and cloud formation occurs, there is also an additional latent heat flux. Heat transport in cloudy Rayleigh-Bénard convection depends on turbulent flow as well as the microphysical state of the clouds: specifically, whether substantial supersaturations exist and whether cloud liquid water is removed through sedimentation/precipitation. In this article we bridge between the Rayleigh-Bénard convection literature and the atmospheric literature. We express the governing equations for cloudy convection in dimensionless form, thereby explicitly identifying the governing parameters relevant to the cloudy case, including Schmidt, Damköhler, supersaturation, and sedimentation numbers. We further connect to the atmospheric literature by obtaining a Nusselt number (dimensionless heat flux) for a cloud-convection system, directly from the conservation equations for temperature and water vapor. This flux has the same form as that identified by Zhang et al. [L. Zhang, K. L. Chong, and K.-Q. Xia, J. Fluid Mech. 874, 1041 (2019)] for convection with water vapor, but is extended to the cloudy case. For equal thermal and water vapor diffusivities, the flux corresponds to the widely used atmospheric quantities equivalent temperature and moist static energy. Using large eddy simulation (LES) of an idealized cloudy Rayleigh-Bénard convection system with fixed boundary conditions, we find that the equivalent heat flux (Nusselt number) is only weakly dependent on the microphysical details of the system, such as liquid water mixing ratio and cloud droplet number concentration. Finally, from the results, we show the vertical profiles of sensible and latent heat fluxes depend on the liquid water content, whereas the equivalent heat flux remains a constant throughout the height of the chamber.

54 ENVIRONMENTAL SCIENCES↗

River and hyporheic zone water geochemical data from OsmoSamplers, East River Pumphouse, Colorado, Nov 2017-Sept 2018

This data package contains geochemical and river water temperature data from OsmoSamplers deployed at East River, Colorado pump house. There are three data files. The first one contains sulfate (SO4) and chloride (Cl) concentrations from riverwater and hyporheic zone (sediment water interface (SWI), 4 cm below seafloor (cmbsf), and 12 (cmbsf)). The second file contains methane concentrations, methane stable carbon isotope ratios and water isotopes from hyporheic zone porewaters. And the third is from a temperature logger during the deployment. Files are provided as .xls or .csv. This research was performed as part of the SBR funded project “Quantifying Subsurface Biogeochemical Variability in a High Altitude Watershed During Winter Isolation” DE-SC0018328. The novel part of this dataset is that we quantify these geochemical parameters throughout the winter isolation period, which is difficult to measure, as well as within the hyporheic zone. The data files were updated 3/1/2021 because the column label for the water isotopes was incorrect. Also, the csv files were also updated since they were not formatted correctly.

54 ENVIRONMENTAL SCIENCES↗

Removal of Tc-99, Zr-95, and Nb-95, From Solutions Obtained After Dissolution of Irradiated Mo Targets

Decontamination of 99 Tc, Nb, and Zr impurities in dissolved irradiated Mo disks can be accomplished using Fe(II) precipitation. Here, we report bench-scale experiments and large-scale demonstrations on removal of 99 Tc (0.1 mM), 95 Nb, and 95 Zr from dissolved Mo disk simulant solutions. Tc removal is accomplished through the reduction and simultaneous immobilization of Tc(VII) by Fe(II), producing an insoluble, Tcincorporated Fe(II)-Fe(III) solid that is removed by filtration. Large-scale testing showed that Tc (97.6% ± 1.7%) is removed without affecting 99 Mo yields. Other important side reaction product impurities in irradiated Mo targets, namely various isotopes of Nb and Zr, are also removed (>99%) in this process. The effects of metal (Fe, Tc, Mo) concentrations, Fe(II)/Fe(III) ratio, pH, temperature, Fe addition method, and hydrogen peroxide addition were tested. The minimum amount of Fe(II) needed to remove up to 99% Tc is 10 mM and the optimal pH value for simultaneous removal of Tc, Nb, and Zr impurities is pH 13.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Reflectance and transmittance characteristics of several selected green and blue-green unialgae.

Obtained reflectance properties of green and blue-green unialgae are evaluated for determining the feasibility of using selected wavelengths in differentiating between green and blue-green algae. The attempt is made to establish selected wavelengths and ratios that would delineate relative concentrations of the algal suspensions. The results should prove helpful in the selection of spectral bands usable in conjunction with multispectrum scanners for qualitative and quantitative studies of algae in bodies of water.

Gramms, L. C.↗

Normal injection of helium from swept struts into ducted supersonic flow

Recent design studies have shown that airframe-integrated scramjets should include instream mounted, swept-back strut fuel injectors to obtain short combustors. Because there was no data in the literature on mixing characteristics of swept strut fuel injectors, the present investigation was undertaken to provide such data. This investigation was made with two swept struts in a closed duct at Mach number of 4.4 and nominal jet-to-air mass flow ratio of 0.029 with helium used to simulate hydrogen fuel. The data is compared with flat plate mounted normal injector data to obtain the effect of swept struts on mixing. Three injector patterns were evaluated representing the range of hole spacing and jet-to-freestream dynamic pressure ratio of interest. Measured helium concentration, pitot pressure, and static pressure in the downstream mixing region are used to generate contour plots necessary to define the mixing region flow field and the mixing parameters.

Mcclinton, C. R.↗

Lidar measurements of two intense stratospheric dust layers

Lidar measurements were made of two stratospheric dust layers on November 26, 1974, using the NASA 48-inch laser radar system. The dust was probably of volcanic origin. The measurements, made at a wavelength of 0.6943 micron, indicated a 6-km thick layer centered at an altitude of 16 km, and a 1.5-km thick layer centered at 20.25 km. The abnormal scattering ratios, scattering functions, and particle concentrations were evaluated. Measurements made on November 28 showed that both layers had considerably diminished.

Mccormick, M. P.↗

Review of measurement and testing problems

Good instrumentation was required to obtain reliable and repeatable baseline data. Problems that were encountered in developing such a total system were: (1) accurate airflow measurement, (2) precise fuel flow measurement, and (3) the instrumentation used for pollutant measurement was susceptible to frequent malfunctions. Span gas quality had a significant effect on emissions test results. The Spindt method was used in the piston aircraft emissions program. The Spindt method provided a comparative computational procedure for fuel/air ratio based on measured emissions concentrations.

Source record↗

The mechanics of ringed basin formation

The study investigates the mechanics of ring formation in lunar basins by collapse or slumping. Two classes of models are presented in order to broaden the range of plausible mechanisms involved. Extrusion flow models which assume a weak layer underlying a strong layer as well as plastic flow models which assume a continuous decrease of cohesion strength with depth are considered. In both classes, strength or resistance to deformation decreases with depth. If this decrease is rapid enough, in either set of models, at least one concentric fault scarp forms. The ratio between the scarp radius and the crater radius varies between 1.2 and about 2.7 depending on the model, and is thus in the range of observed radius ratios.

Melosh, H. J.↗