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At least 217 records · Page 12

Organic Matter in Extraterrestrial Water-Bearing Salt Crystals

Introduction: Direct samples of early Solar System fluids are present in two thermally-metamorphosed ordinary chondrite regolith breccias (Monahans (1998) [H5] and Zag [H3-6]), which were found to contain brine-bearing halite (NaCl) crystals that have been added to the regolith of an S-type asteroid following asteroidal metamorphism [1, 2]. The brine-bearing halite grains were proposed to be formed on an icy C-type asteroids (possibly Ceres), and transferred to an S-type asteroid via cryovolcanic event(s) [3]. A unique aspect of these halites is that they contain abundant organic rich solid inclusions hosted within the halites alongside the water inclusions. Methods: We analyzed in detail the compositions of the organic solids and the amino acid content of the halite crystals with two-step laser desorption/laser ionization mass spectrometry (L(sup 2) MS), Raman spectroscopy, X-ray absorption near edge structure (XANES), nanoscale secondary ion mass spectrometry (NanoSIMS), and ultra-performance liquid chromatography fluorescence detection and quadrupole time of flight hybrid mass spectrometry (UPLC-FD/QToF-MS). Results and Discussion: The L(sup 2) MS results show signatures of low-mass polyaromatic hydro-carbons (PAHs) indicated by sequences of peaks separated by 14 atomic mass units (amu) due to successive addition of methylene (CH2) groups to the PAH skeletons [4]. Raman spectra of the micron-sized solid inclusions of the halites indicate the presence of abundant and highly variable organic matter that include a mixture of short-chain aliphatic compounds and macromolecular carbon. C-XANES analysis identified C-rich areas with peaks at 285.0 eV (aromatic C=C) and 286.6 eV (vinyl-keto C=O). However, there is no 1s-sigma* exciton peak (291.7 eV) that is indicative of the development of graphene structure [5], which suggests the organics were synthesized cold. Na-noSIMS analyses show C-rich and N-rich areas that exhibit similar isotopic values with that of the IOM in the unweathered CR chondrites and less metamorphosed meteorites [6], and are moderately enriched in N-15 (delta N-15 = 106.1-164.5 per mille). The total amino acid distribution and abundance of the Zag matrix (approximately 1,940 parts per billion [ppb]) is comparable to other ordinary chondrites (60-3,330 ppb) [7, 8]. While the Zag matrix is gamma-ABA and EACA-deficient, the halite is shown to exhibit an opposite trend and is almost depleted in amino acids. The striking difference in the amino acid contents between the halite and matrix indicates their separate synthetic origins. Conclusion: Abundant, primitive, and highly-diverse N-15-rich organic compounds were detected in brine-water bearing halite crystals that were synthesized on a cryovolcanically-active asteroid. Our study suggests that the asteroidal parent body where the halite precipitated, potentially Ceres, is a host to abundance large variety organic precursors. Insoluble organic matter and amino acids can be synthesized from similar organic precusors under hydrous conditions [9].We envision that similar organic synthetic processes could have occurred on Ceres that synthesized organic solids as well as biologically relevant molecules.

Chan, Q. H. S.↗

Removal of Residual Chromium from Aluminum Oxide by Containerless Liquid-phase Processing

Berneuil sapphire was purified of Cr 3+ by containerless melting and processing at ca. 2550 K in high purity argon, dry air and pure oxygen. Recovered material was examined by laser induced fluorescence and Raman spectroscopy. The Cr 3+ fluorescence intensity decreased in processed specimens at rates proportional to the chromium concentration and p(O 2 ) 0.21 . The initial chromium concentration was ca. 5 ppm and decreased by factors of ca. 50, 3000, and 2x10 5 after processing for 300 seconds in argon, air and oxygen, respectively. Evidence is presented that the Cr 3+ was removed predominantly as CrO 2 (g) and not by conversion to other oxidation states of chromium in the condensed phase. A comparison of the Raman peak shifts for as-received and processed samples indicates that considerable stress was retained during containerless solidification of the highly undercooled melts.

sapphire↗

Heating Experiments of the Tagish Lake Meteorite: Investigation of the Effects of Short-Term Heating on Chondritic Organics

We present in this study the effects of short-term heating on organics in the Tagish Lake meteorite and how the difference in the heating conditions can modify the organic matter (OM) in a way that complicates the interpretation of a parent body's heating extent with common cosmo thermometers. The kinetics of short-term heating and its influence on the organic structure are not well understood, and any study of OM is further complicated by the complex alteration processes of the thermally metamorphosed carbonaceous chondrites - potential analogues of the target asteroid Ryugu of the Hayabusa2 mission - which had experienced post-hydration, short-duration local heating. In an attempt to understand the effects of short-term heating on chondritic OM, we investigated the change in the OM contents of the experimentally heated Tagish Lake meteorite samples using Raman spectroscopy, scanning transmission X-ray microscopy utilizing X-ray absorption near edge structure spectroscopy, and ultra-performance liquid chromatography fluorescence detection and quadrupole time of flight hybrid mass spectrometry. Our experiment suggests that graphitization of OM did not take place despite the samples being heated to 900 degrees Centigrade for 96 hours, as the OM maturity trend was influenced by the nature of the OM precursor, such as the presence of abundant oxygenated moieties. Although both the intensity of the 1s-sigma σ* exciton cannot be used to accurately interpret the peak metamorphic temperature of the experimentally heated Tagish Lake sample, the Raman graphite band widths of the heated products significantly differ from that of chondritic OM modified by long-term internal heating.

Chan, Queenie Hoi Shan↗

Investigation of the feasibility of CARS measurements in scramjet combustion

Results are presented of analytical and experimental investigations to determine the feasibility of using coherent anti-Stokes Raman Spectroscopy (CARS) to measure temperature and species concentration in supersonic combustion experiments. The CARS spectra of H2O, O2 and H2 were measured in laboratory flames. Computer code calculated spectra agree very well with the measured spectra. Temperature, and O2 and H2 concentration profiles have been determined from CARS spectra in a laboratory H2 air flat diffusion flame. Temperature measurements agree with radiation corrected thermocouple measurements within 5 to 10 percent, depending on species concentration. The feasibility of measuring O2 concentrations up to 10 percent, from the spectral shape was demonstrated. H2 concentrations determined from CARS intensities agree with spontaneous Raman measurements within a factor of two. Finally, a conceptual design was formulated for diagnostics in the Langley Research Center scramjet combustion facility.

Shirley, J. A.↗

Raman-atomic force microscopy of the ommatidial surfaces of Dipteran compound eyes

The ommatidial lens surfaces of the compound eyes in several species of files (Insecta: Diptera) and a related order (Mecoptera) were analyzed using a recently developed Raman-atomic force microscope. We demonstrate in this work that the atomic force microscope (AFM) is a potentially useful instrument for gathering phylogenetic data and that the newly developed Raman-AFM may extend this application by revealing nanometer-scale surface chemistry. This is the first demonstration of apertureless near-field Raman spectroscopy on an intact biological surface. For Chrysopilus testaceipes Bigot (Rhagionidae), this reveals unique cerebral cortex-like surface ridges with periodic variation in height and surface chemistry. Most other Brachyceran flies, and the "Nematoceran" Sylvicola fenestralis (Scopoli) (Anisopodidae), displayed the same morphology, while other taxa displayed various other characteristics, such as a nodule-like (Tipula (Triplicitipula) sp. (Tipulidae)) or coalescing nodule-like (Tabanus punctifer Osten Sacken (Tabanidae)) morphology, a smooth morphology with distinct pits and grooves (Dilophus orbatus (Say) (Bibionidae)), or an entirely smooth surface (Bittacus chlorostigma MacLachlan (Mecoptera: Bittacidae)). The variation in submicrometer structure and surface chemistry provides a new information source of potential phylogenetic importance, suggesting the Raman-atomic force microscope could provide a new tool useful to systematic and evolutionary inquiry.

Eye/ultrastructure↗

Nanowire Electron Scattering Spectroscopy

Nanowire electron scattering spectroscopy (NESS) has been proposed as the basis of a class of ultra-small, ultralow-power sensors that could be used to detect and identify chemical compounds present in extremely small quantities. State-of-the-art nanowire chemical sensors have already been demonstrated to be capable of detecting a variety of compounds in femtomolar quantities. However, to date, chemically specific sensing of molecules using these sensors has required the use of chemically functionalized nanowires with receptors tailored to individual molecules of interest. While potentially effective, this functionalization requires labor-intensive treatment of many nanowires to sense a broad spectrum of molecules. In contrast, NESS would eliminate the need for chemical functionalization of nanowires and would enable the use of the same sensor to detect and identify multiple compounds. NESS is analogous to Raman spectroscopy, the main difference being that in NESS, one would utilize inelastic scattering of electrons instead of photons to determine molecular vibrational energy levels. More specifically, in NESS, one would exploit inelastic scattering of electrons by low-lying vibrational quantum states of molecules attached to a nanowire or nanotube.

Hunt, Brian↗

A parametric study of single-wall carbon nanotube growth by laser ablation

Results of a parametric study of carbon nanotube production by the double-pulse laser oven process are presented. The effect of various operating parameters on the production of single-wall carbon nanotubes (SWCNTs) is estimated by characterizing the nanotube material using analytical techniques, including scanning electron microscopy, transmission electron microscopy, thermo gravimetric analysis and Raman spectroscopy. The study included changing the sequence of the laser pulses, laser energy, pulse separation, type of buffer gas used, operating pressure, flow rate, inner tube diameter, as well as its material, and oven temperature. It was found that the material quality and quantity improve with deviation from normal operation parameters such as laser energy density higher than 1.5 J/cm2, pressure lower than 67 kPa, and flow rates higher than 100 sccm. Use of helium produced mainly small diameter tubes and a lower yield. The diameter of SWCNTs decreases with decreasing oven temperature and lower flow rates.

Nanotubes, Carbon/chemistry↗

Fullerenes in an impact crater on the LDEF spacecraft

The fullerenes C60 and C70 have been found to occur naturally on Earth and have also been invoked to explain features in the absorption spectra of interstellar clouds. But no definitive spectroscopic evidence exists for fullerenes in space and attempts to find fullerenes in carbonaceous chondrites have been unsuccessful. Here we report the observation of fullerenes associated with carbonaceous impact residue in a crater on the Long Duration Exposure Facility (LDEF) spacecraft. Laser ionization mass spectrometry and Raman spectroscopy indicate the presence of fullerenes in the crater and in adjacent ejecta. Man-made fullerenes survive experimental hypervelocity (approximately 6.1 km s-1) impacts into aluminium targets, suggesting that space fullerenes contained in a carbonaceous micrometeorite could have survived the LDEF impact at velocities towards the lower end of the natural particle encounter range (<13 km s-1). We also demonstrate that the fullerenes were unlikely to have formed as instrumental artefacts, nor are they present as contaminants. Although we cannot specify the origin of the fullerenes with certainty, the most plausible source is the chondritic impactor. If, alternatively, the impact produced the fullerenes in situ on LDEF, then this suggests a viable mechanism for fullerene production in space.

long duration↗

Microstructural Changes and Pb Mobility During the Zircon to Reidite Transformation: Implications for Planetary Impact Chronology

Impact events modify and leave behind a complex history of rock metamorphism on terrestrial planets. Evidence for an impact event may be recorded in physical changes to minerals, such as mineral deformation and formation of high P-T polymorphs, but also in the form of chemical fingerprints, such as enhanced elemental diffusion and isotopic mixing. Here we explore laboratory shock-induced physical and chemical changes to zircon and feldspar, the former of which is of interest because its trace elements abundances and isotope ratios are used extensively in geochemistry and geochronology. To this end, a granular mixture of Bishop Tuff sanidine and Kuehl Lake zircon, both with well characterized Pb isotope compositions, was prepared and then shocked via a flat plate accelerator. The peak pressure of the experiment, as calculated by the impedance matching method, was ~24 GPa although a broader range of P-T conditions is anticipated due to starting sample porosity. Unshocked and shocked materials were characterized via scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and Raman spectroscopy. These methods show that the starting zircon material had abundant metamict regions, and the conversion of the feldspar to glass in the post-shock material. Analyses of the shocked product also yielded multiple occurrences of the high-pressure ZrSiO 4 polymorph reidite, with some domains up to 300 μm across. The possibility of U-Pb system disturbance was evaluated via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ion mass spectrometry (SIMS). The isotopic data reveal that disturbance of the U-Pb geochronometer in the reidite was minimal (<2% for the main U-Pb geochronometers). To better constrain the P-T conditions during the shock experiment, we complement impedance matching pressure calculations with iSALE2D impact simulations. The simulated results yield a range of P-T conditions experienced during the experiment and show that much of the sample may have reached >30 GPa, which is consistent with formation of reidite. In the recovered shocked material, we identified lamellae of reidite, some of which interlock with zircon lamellae. Reidite {112} twins were identified, which we interpret to have formed to reduce stress between the crystal structure of the host zircon and reidite. These two findings support the interpretation that shear transformation enabled the transition of zircon to reidite. The size and presence of reidite found here indicate that this phase is probably common in impact-shocked crustal rocks that experienced ~25 to ~35 GPa, especially when the target material has porosity. Additionally, shock loading of the zircon and transformation to reidite at these pressures in porous materials is unlikely to significantly disturb the U-Pb system in zircon and that the reidite inherits the primary U and Pb elemental and isotopic ratios from the zircon.

Bishop Tuff↗

Planetary astronomy program

Visual photometric function data for Saturn's rings were analyzed in terms of elementary anisotropic scattering radiative transfer models which involve the Henyey-Greenstein function. Limits were placed on the combinations of single scattering albedo, and backscattering directivity, which are permitted by observation. Particles with lunar-like scattering properties were excluded by the analysis. Results are consistent with the ring particles being more-or-less pure, and spherical, conglomerates of H2O frost. Multicolor (5500 A-7600 A), narrow band (100 A), area scanning photometry was used to study the wavelength variation in the optical appearance of Uranus. Limb brightening was detected in two CH4 bands, i.e. 6190A and 7300A. Spectrophotometric observations and analysis of the asteroids and Raman spectroscopy of the atmosphere of Uranus are also briefly discussed.

Source record↗

Instrumentation techniques for studying heterogeneous combustion

Velocity measurements in flames and the simultaneous measurement of droplet size and velocity with the aid of laser anemometry are considered along with methods of particle size measurement and techniques based on laser Raman spectroscopy. Attention is given to high-speed photography and holography, computer compensated thermocouples, and the determination of turbulence characteristics. The employment of suction probes is also discussed, taking into account sampling methods, the effects of temperature change in sampling probes on particle formation, and the chemical analysis of samples.

Chigier, N. A.↗

A 100 microsec, reliable, 10 Hz pulsed supersonic molecular beam source

A 10-Hz repetition rate, 100-microsec duration, reliable pulsed supersonic molecular beam source is described. Mechanical and electrical design of the pulsed valve are given in detail. Characteristics of the supersonic expansion obtained using coherent anti-Stokes Raman spectroscopy in acetylene are presented. They include pulse shape, gas rotational and translational cooling as a function of distance from the nozzle, clustering effects, and shock heating at the leading edge of the pulse.

Byer, R. L.↗

CARS temperature measurements in the fuel preburner of the Space Shuttle main engine: A feasibility study

This report discusses the feasibility of making temperature profile measurements in the fuel preburner of the main engine of the space shuttle (SSME) using coherent anti-Stokes Raman spectroscopy (CARS). The principal thrust of the work is to identify problems associated with making CARS measurements in high temperature gas phase hydrogen at very high pressures (approx 400 atmospheres). To this end a theoretical study was made of the characteristics of the CAR spectra of H2 as a function of temperature and pressure and the accuracy with which temperatures can be extracted from this spectra. In addition the experimental problems associated with carrying out these measurements on a SSME at NSTL were identified. A conceptual design of a CARS system suitable for this work is included. Many of the results of the calculations made in this report are plotted as a function of temperature. In the course of presenting these results, it was necessary to decide whether the number of density or the pressure should be treated as a fixed parameter.

Beiting, E. J.↗

Comparison of CARS combustion temperatures with standard techniques

This paper describes a comparative study of temperatures measured with Coherent Anti-Stokes Raman Spectroscopy (CARS) and those using standard measurement techniques. CARS temperatures from nitrogen vibrational-rotational spectra have been obtained in a premixed hydrogen-air laboratory flame supported on a flat flame burner over a temperature range from about 1000 K to 2100 K. The techniques used for comparison were sodium line reversal, thin wire thermocouples and heat balance calculations. These studies show a good agreement over the entire temperature range studied.

Antcliff, R. R.↗

Coherent Anti-Stokes Raman scattering with reflective optics

Attention is given to the implementation of a novel reflective optics configuration in which the lens normally employed for focusing and crossing the input laser beams in Coherent Anti-Stokes Raman spectroscopy (CARS) is replaced by a spherical mirror, allowing large crossing angles to be obtained with a single focusing device and permitting the laser generation and collection equipment to be located on one side of the sample region. The experimental results obtained demonstrate the feasibility of mirror-based CARS in remote combustion diagnostics.

Antcliff, R. R.↗

Characterization and measurement of polymer wear

Analytical tools which characterize the polymer wear process are discussed. The devices discussed include: visual observation of polymer wear with SEM, the quantification with surface profilometry and ellipsometry, to study the chemistry with AES, XPS and SIMS, to establish interfacial polymer orientation and accordingly bonding with QUARTIR, polymer state with Raman spectroscopy and stresses that develop in polymer films using a X-ray double crystal camera technique.

Buckley, D. H.↗

Raman structural studies of the nickel electrode

Raman spectroscopy is sensitive to empirically controlled nickel electrode structural variations, and has unique potential for structural characterization of these materials. How the structure relates to electrochemical properties is examined so that the latter can be more completely understood, controlled, and optimized. Electrodes were impregnated and cycled, and cyclic voltammetry is being used for electrochemical characterization. Structural variation was observed which has escaped detection using other methods. Structural changes are induced by: (1) cobalt doping, (2) the state of change or discharge, (3) the preparation conditions and type of buffer used, and (4) the formation process. Charged active mass has an NiOOH-type structure, agreeing with X-ray diffraction results. Discharged active mass, however, is not isostructural with beta-Ni(OH)2. Chemically prepared alpha phases are not isostructural either. A disordered structural model, containing point defects, is proposed for the cycled materials. This model explains K(+) incorporation. Band assignments were made and spectra interpreted for beta-Ni(OH)2, electrochemical NiOOH and chemically precipitated NiOOH.

Cornilsen, B. C.↗