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At least 397 records · Page 22

The Origin of Dark Inclusions in Allende: New Evidence from Lithium Isotopes

Aqueous and thermal processing of primordial material occurred prior to and during planet formation in the early solar system. A record of how solid materials were altered at this time is present in the carbonaceous chondrites, which are naturally delivered fragments of primitive asteroids. It has been proposed that some materials, such as the clasts termed dark inclusions found in type III chondrites, suggest a sequence of aqueous and thermal events. Lithium isotopes (Li-6 and Li-7) can reveal the role of liquid water in dark inclusion history. During aqueous alteration, Li-7 passes preferentially into solution leaving Li-6 behind in the solid phase and, consequently, any relatively extended periods of interaction with Li-7-rich fluids would have left the dark inclusions enriched in the heavier isotope when compared to the meteorite as a whole. Our analyses of lithium isotopes in Allende and its dark inclusions reveal marked isotopic homogeneity and no evidence of greater levels of aqueous alteration in dark inclusion history.

Sephton, Mark A.↗

Deuterium Fractionation in Analogs of Interstellar Ices: Laboratory Measurements

A question of key interest in the field of Astrobiology is the extent to which organic compounds made in space may play a role in the origin of life in planetary systems. In general, the best proof that at least some interstellar materials survive incorporation into forming stellar/planetary systems is their identification in extraterrestrial samples through detection of the isotopic anomalies they may carry. In the case of organic compounds, the chief isotopic anomalies that might be expected are the enrichment of D and 15N. and such enrichments are seen in primitive extraterrestrial materials, for example, in the organics in carbonaceous chondrites and interplanetary dust particles. In my talk I will review the various astrochemical processes by which deuterium can become enriched in organic compounds and will discuss some recent laboratory experiments that examine one of these processes in particular. name]y the UV photolysis of interstellar ices. Finally, I will review the current state of our knowledge of D enrichments in primitive solar system materials and discuss the constraints these data place on the relative importance of the various possible interstellar D enrichment processes.

Sandford, Scott A.↗

Catalysts by pyrolysis: Direct observation of transformations during re-pyrolysis of transition metal-nitrogen-carbon materials leading to state-of-the-art platinum group metal-free electrocatalyst

Transition metal-nitrogen-carbon (M-N-C) materials have been the focus of scientists’ efforts to address the rising need for earth-abundant materials solutions for energy technology and decarbonization of the economy. They are viewed as one of the most promising candidates to replace platinum group metal (PGM) catalysts in the fuel cell and energy conversion fields, including the application of oxygen reduction reaction, carbon dioxide reduction reaction, and nitrogen reduction reaction. In the effort to improve M-N-C materials properties and achieve atomic dispersity of the transition metal in the carbonaceous matrix, a re-pyrolysis process has been proposed. This secondary heat treatment process of already obtained primary pyrolysis-derived M-N-C materials has been widely reported to substantially improve the electrochemical performance and operational stability of the catalysts. Here, we report a systematic investigation of this process used on samples of templated M-N-C catalysts to obtain state-of-the-art catalysts via in situ heating X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), and X-ray computed tomography (CT) characterization methods. It is found that the re-pyrolysis of M-N-C materials could result in the partial amorphization of the carbonaceous substrate. It causes the rearrangement and transformation of multitudinous N moieties, leading to optimization of their morphological display and association with atomically dispersed transition metal dopants. Ultimately, the re-pyrolysis results in an increase in uniformity of the active Fe-Nx sites distribution without the formation of nano-crystalline phases (metallic or carbide) and with overall preservation of the morphology of the carbonaceous framework achieved during the first formative pyrolysis step of the templated synthesis. Finally, these observations provide confirmation that empirically established re-pyrolysis is recommended to be used on all M-N-C materials despite the different synthesis routes to obtain a practical advanced catalytic material.

36 MATERIALS SCIENCE↗

The low-temperature electrical properties of carbonaceous meteorites

Electrical conductivities and dielectric constants have been measured over the temperature range 90-300 K on several carbonaceous chondrites and some terrestrial analogues. The conductivities of meteorites of different petrologic subtypes range over many orders of magnitude and the low-temperature activation energies are typically much smaller than those observed in terrestrial materials at higher temperatures. The electrical properties of carbonaceous chondrites vary systematically with chemical-mineralogical characteristics in that: (1) activation energy at low temperature is greater in the more volatile-rich meteorites containing hydrated silicates, and (2) conductivity is greater in the more reduced meteorites of higher petrologic subtype. These new data on the electrical properties of chondrites hold important implications for both the thermal and magnetic histories of small bodies in the early solar system.

Brecher, A.↗

Adsorption and Desorption of Carbon Dioxide and Water Mixtures on Synthetic Hydrophobic Carbonaceous Adsorbents

Several synthetic carbonaceous adsorbents produced through pyrolysis of polymeric materials are available commercially. Some appear to have advantages over activated carbon for certain adsorption applications. In particular, they can have tailored hydrophobicities that are significantly greater than that of activated carbon, while moderately high surfaces areas are retained. These sorbents are being investigated for possible use in removing trace contaminants and excess carbon dioxide from air in closed habitats, plant growth chambers, and other applications involving purification of humid gas streams. We have analyzed the characteristics of a few of these adsorbents through adsorption and desorption experiments and standard characterization techniques. This paper presents pure and multicomponent adsorption data collected for carbon dioxide and water on two synthetic carbonaceous adsorbents having different hydrophobicities and capillary condensation characteristics. The observations are interpreted through consideration of the pore structure and surface chemistry of the solids and interactions between adsorbed carbon dioxide, water, and the solvent gas.

Finn, John E.↗

Contribution of Ryugu-like material to Earth’s volatile inventory by Cu and Zn isotopic analysis

We report initial analyses showed that asteroid Ryugu’s composition is close to CI (Ivuna-like) carbonaceous chondrites (CCs) – the chemically most primitive meteorites, characterized by near-solar abundances for most elements. However, some isotopic signatures (for example, Ti, Cr) overlap with other CC groups, so the details of the link between Ryugu and the CI chondrites are not yet fully clear. Here we show that Ryugu and CI chondrites have the same zinc and copper isotopic composition. As the various chondrite groups have very distinct Zn and Cu isotopic signatures, our results point at a common genetic heritage between Ryugu and CI chondrites, ruling out any affinity with other CC groups. Since Ryugu’s pristine samples match the solar elemental composition for many elements, their Zn and Cu isotopic compositions likely represent the best estimates of the solar composition. Earth’s mass-independent Zn isotopic composition is intermediate between Ryugu/CC and non-carbonaceous chondrites (NCs), suggesting a contribution of Ryugu-like material to Earth’s budgets of Zn and other moderately volatile elements.

58 GEOSCIENCES↗

Are carbonaceous chondrites primitive or processed - A review

According to the results of the present analysis, carbonaceous chondrites are obviously not pristine samples of proto-solar-system condensates. In terms of chemistry, however, these chondrites may represent the most primitive solar system materials known. It appears that the alterations experienced by carbonaceous chondrites were isochemical, or nearly so, so that their bulk compositions have remained practically unchanged, provided that the analyses are representative of large portions of the meteorites.

Mcsween, H. Y., Jr.↗

Irradiated Benzene Ice Provides Clues to Meteoritic Organic Chemistry

Aromatic hydrocarbons account for a significant portion of the organic matter in carbonaceous chondrite meteorites, as a component of both the low molecular weight, solvent-extractable compounds and the insoluble organic macromolecular material. Previous work has suggested that the aromatic compounds in carbonaceous chondrites may have originated in the radiation-processed icy mantles of interstellar dust grains. Here we report new studies of the organic residue made from benzene irradiated at 19 K by 0.8 MeV protons. Polyphenyls with up to four rings were unambiguously identified in the residue by gas chromatography-mass spectrometry. Atmospheric pressure photoionization Fourier transform mass spectrometry was used to determine molecular composition, and accurate mass measurements suggested the presence of polyphenyls, partially hydrogenated polyphenyls, and other complex aromatic compounds. The profile of low molecular weight compounds in the residue compared well with extracts from the Murchison and Orgueil meteorites. These results are consistent with the possibility that solid phase radiation chemistry of benzene produced some of the complex aromatics found in meteorites.

benzene↗

Carbon in the outer solar system

The satellites of Uranus, with densities between 1.3 and 1.7 g cm(-3) (from Voyager 2 observations) and the Pluto-Charon system, with a mean density of just above 1.8 g cm(-3) (from terrestrial observations of mutual eclipse events), are too dense to have a significant amount of methane ice in their interiors. However, the observed densities do not preclude contributions from such organic materials as the acid-insoluble residue in carbonaceous chondrites and laboratory-produced tholins, which have densities on the order of approximately 1.5 g cm(-3). These and other considerations have led researchers to investigate the carbon mass budget in the outer solar system, with an emphasis on understanding the contribution of organic materials. Modeling of the interiors of Pluto and Charon (being carried out by R. Reynolds and A. Summers of NASA/Ames), assuming rock and water ice as the only constituents, suggests a silicate mass fraction for this system on the order of 0.65 to 0.70. The present work includes the most recent estimates of the C/H enhancements and high z/low z ratios of the giant planets (Pollack and Bodenheimer, 1987), and involves a more careful estimation of the high z/low z mass ratio expected from solar abundances than was used in Pollack et al. (1986), including the influence of the fraction of C in CO on the amount of condensed water ice. These calculations indicate that for a particular fraction of C in CO and a given fraction of C-bearing planetesimals that dissolve in the envelope (most likely in the range 0.50 to 0.75), (1) Jupiter and Saturn require a larger fraction of C in condensed materials than Uranus and Neptune, but (2) the Jupiter and Saturn results are much less strongly constrained by the error bars on the observed C/H enhancements and high z/low z ratios than is the case for Uranus and Neptune. The clearest result is that in the region of the solar nebula near Uranus and Neptune, the minority of carbon that is not in gaseous CO (1) must include a nonzero amount of condensed material, but (2) is most likely not condensed material alone, i.e., there must be a third carbon-bearing component besides condensed material and gaseous CO. Given the implied dearth of methane ice, the condensed carbon is likely dominated by organic material, and the third component present in addition to CO and organics is assumed to be CH4 gas.

Simonelli, D. P.↗

Metamorphosed CM and CI Carbonaceous Chondrites Could Be from the Breakup of the Same Earth-crossing Asteroid

Far from being the relatively unprocessed materials they were once believed to be, we now know that a significant number of carbonaceous chondrites were thermally metamorphosed on their parent asteroid(s). Numerous studies indicate that 7 "CM" and 2 "CI" chondrites have been naturally heated, variously, at from 400 to over 700 C on their parent asteroid(s). Petrographic textures reveal that this thermal metamorphism occurred after the dominant aqueous alteration phase, although some meteorites show evidence of a heating event between two aqueous alteration episodes, i.e. pro- and retrograde aqueous alteration. Aside from the issues of the identification of the transient heat source, timing of metamorphism, and the relation of these materials (if any) to conventional CM and CI chondrites, there is also a mystery related to their recovery. All of these meteorites have been recovered from the Antarctic; none are falls or finds from anyplace else. Indeed, the majority have been collected by the Japanese NIPR field parties in the Yamato Mountains. In fact, one estimate is that these meteorites account for approx. 64 wt% of the CM carbonaceous chondrites at the NIPR. The reasons for this are unclear and might be due in part to simple sampling bias. However we suggest that this recovery difference is related to the particular age of the Yamato Mountains meteorite recovery surfaces, and differences in meteoroid fluxes between the Yamato meteorites and recent falls and substantially older Antarctic meteorites. Additional information is included in the original extended abstract.

Zolensky, Michael↗

Organic Nano-Grains in Comet 103P/Hartley 2: The Organic Glue of Porous Aggregate Grains?

The GNIRS instrument on the Gemini 8-­‐m telescope observed comet 103P/Hartley on 2010-­‐ Dec-­‐04UT, a month after the EPOXI Mission encounter, and detected the 3.3 and 3.4 um bands in emission. The 3.3/3.4 ratio and the broad band widths are consistent with experiments of heated (approximately 600 K) aliphatic carbon (-CH3, -CH2) thin films. For the 3.4 micron band to be in emission, the aliphatic bonds must be attached to a carrier possessing the strongly UV-­‐absorbing C=C aromatic rings, and these rings have to be less than 50-­‐100 carbon atoms (4-6 Angstrom) for attached -CH bonds to also generate a 3.3 micron-band in emission. Slightly larger (≥10Å) Very Small Grains (VSGs) can absorb single UV photons comparable to or exceeding their heat capacity, thermally fluctuate and release IR photon(s). The 3.3 micron and 3.4 micron bands observed by GNIRS suggest that organic macromolecules/ nano-­‐grains with both aliphatic and aromatic bonds are fluorescing/thermally fluctuating in the coma. Aliphatic and aromatic materials have been seen in Stardust samples and the primitive carbonaceous chondrite 'Tagish Lake'. The larger the ratio of the -CH2/-CH3 components of the aliphatic 3.4 micron band, the more 'primitive' the organic material. In a Stardust organic globule, some aliphatic bonds were transformed into aromatic bonds during the low dosage of Transmission Electron Microscope imaging. Conversely, lab experiments show irradiation of ices containing small PAHs generates aliphatic organics. Photo-­‐processing of ices also likely forms the ubiquitous aliphatic coatings that appear on the surfaces of all silicate subgrains constituting nine cometary interplanetary dust particles. The aliphatic coatings, dominated by -CH2, likely were important in sticking the aggregates together, and existed prior to incorporation of dust aggregates into comet nuclei. These comet aliphatics may be some of the sought-­‐after precursors to the more robust and complex organics studied as Insoluble Organic Matter in carbonaceous chondrites. Aliphatic coatings on submicron grains, however, will not be observable in absorption because they are fairly transparent, nor do the aliphatic carbonaceous coatings produce the 3.4 micron emission band because the particles they are attached to are too large (too many vibration modes). We must probe the nano-­‐sized organic carriers that undergo substantive thermal fluctuations in cometary comae and emit at 3.3 3.4 micron. Observations of the 3.3 and 3.4 micron emission features contribute to characterizing the evolution of organics prior to their incorporation into cometary nuclei as well as their rapid evolution in cometary comae, which in turn contributes to deepening our understanding of the evolution of organics on the surfaces of asteroids and outer icy bodies in our solar system. Studying organics in comets contributes to understanding the formation and evolution pathways of ISM organics through to the formation of the robust insoluble organic matter in meteorites. A'Hearn, M.F., et al. 2011, Science, 332, 1396; Bockelee-­‐Morvan, D. et al. 1995, Icarus, 116, 18; De Gregorio, B.T., et al. 2010, GCA, 74, 4454; Dello Russo, N., et al. 2011, ApJ, 734, L8; Dischler et al. 1983, Solid State Communications, 48, 105; Flynn, G., et al. 2010a, LPSC, 41, #1079; Flynn, G., et al. 2010b, COSPAR, 38, F31-­‐0012-­‐10; Flynn, G., Wirick, S. 2011, LPSC, 42, #1856; Fomenkova, et al. 1994, GCA 58, 4503; Matrajt, G., et al. 2013, ApJ, 765, 145; Schutte, et al. 1993, ApJ, 415, 397; Wooden, D.H. et al. 2011, EPSC-­‐DPS, 1557; Wooden, D.H. et al. 2013, submitted.

Stardust samples↗

Investigating Space Weathering Effects on Carbonaceous Asteroids Using High-flux and Low-flux Ion Irradiation of the Murchison Meteorite

Airless planetary bodies are continuously altered by space weathering processes such as solar wind irradiation and micrometeoroid bombardment. These processes change the microstructural, chemical, and optical properties of planetary regoliths and, in turn, complicate interpretations of surface composition from remote sensing data. Previous space weathering investigations have focused primarily on lunar and ordinary chondrite materials, the latter of which have been directly linked to S-type asteroids [1]. However, relatively little is known about space weathering of primitive carbonaceous chondrites, which contain a combination of hydrous silicate and organic phases and are hypothesized to be fragments of C-complex asteroids [2]. To address this knowledge gap and maximize the science return of missions targeting C-complex asteroids (e.g., NASA OSIRIS-REx targeting Bennu and JAXA Hayabusa2 targeting Ryugu)[3-4], we examine the spectral, microstructural, and chemical effects of simulated solar wind weathering on a carbonaceous asteroid analog material. Here, we present the results from coordinated analyses of Murchison (CM2) meteorite slabs irradiated with 1 keV/amu H+ and He+ ions.

space weathering↗

15N Fractionation in Star-Forming Regions and Solar System Objects

A central issue for understanding the formation and evolution of matter in the early Solar System is the relationship between the chemical composition of star-forming interstellar clouds and that of primitive Solar System materials. The pristinemolecular content of comets, interplanetary dust particles and carbonaceous chondrites show significant bulk nitrogen isotopic fractionation relative to the solar value, 14N15N 440. In addition, high spatial resolution measurements in primitive materials locally show even more extreme enhancements of 14N15N 100.

pristine molecular content↗

Carbon Tracers of Aqueous Processes: Isotopic Analysis of Cr Carbonate Grains With Implications for Bennu Samples

Carbonate grains in carbonaceous chondrites record aqueous alteration events on the asteroidal parent bodies, including evidence for episodic alteration, timing of alteration, and time and temperature evolution of volatiles. Spectral features in the 3.4 μm region at asteroid Bennu have been interpreted as coming from carbonate minerals. Coordinated analysis of carbonate grains will be a valuable tool for analysis of Bennu samples, and related analysis of analog materials provides important context for understanding aqueous alteration of carbonaceous asteroids more broadly. To that end, our team is analyzing carbonates in Bennu analog materials, using Raman spectroscopy to identify carbonates and assess the maturity of related organic materials, vacuum reflectance spectroscopy from the ultraviolet through thermal infrared range to constrain contributions from carbonates and organics, X-ray microtomography and electron probe microanalysis (EPMA) to assess the distribution of void space, transmission electron microscopy to characterize space weathering effects, and EPMA and secondary ion mass spectrometry (SIMS) to measure composition and isotopic ratios. Here, we describe in situ analysis of carbon and oxygen isotopes from carbonates in Grosvenor Mountains (GRO) 95577.

K E Miller↗

The magnetic effects of brecciation and shock in meteorites. II - The ureilites and evidence for strong nebular magnetic fields. III - The achondrites

Magnetic studies were conducted on samples of the ureilitic meteorites Goalpara, Havero, Novo Urei, and Kenna. Measurements included bulk magnetic susceptibility, natural remanent magnetization (NRM), saturation remanence, and the demagnetization behavior of NRM and saturation remanence. An approximate 'fossil' magnetic field intensity was determined by analysis of coercivity spectra of NRM and saturation remanence after reheating. It was found that the magnetic susceptibility of ureilites increased with severity of shock, and the NRM intensity decreases while its coercivity spectrum generally hardens with increasing shock. Goalpara and Kenna are distinguished by unexpectedly homogeneous, strong, stable, and directionally clustered NRM, indicative of a unique original magnetizing event. The results support the assertion that both ureilites and carbonaceous chondrites have formed from related nebular material and provide further evidence for a strong external magnetic field during the accretional stages and throughout an early bombardment stage.

Brecher, A.↗

Calculation of space station infrared irradiance from atmosphere-induced emissions

The excitation mechanisms and radiance estimates over the 1 to 10 micron region for CO2(v), H2O(v), CO(v), OH(v), NO2(2B-2A) and N2(B3 pi - A3 sigma) are discussed. The infrared irradiance of the Space Station at an altitude of 460 km was estimated. The surface material was presumed to be non-carbonaceous and inert. The determined number densities of the various gases relevant to the Space Station from both ambient and outgassing sources are presented. A model for the production of and emission from the infrared active molecules was constructed that considers two classes of production processes: (1) gas phase excitation of molecules in the near Station environment by collision with ambient flux; and (2) surface processes that lead to molecular excitation. A composite spectrum of all major emitting species shows that the observed irradiance is non-uniform over the 1 to 8 micron region. The comparison of predicted irradiance with the zodiacal background indicates that the Space Station infrared background from atmosphere-induced emissions may be a problem of consequence.

Fraser, M. E.↗

Mineral equilibrium in fractionated nebular systems

We investigated the equilibrium mineral assemblages in chemically fractionated nebular systems, using a computer routine that finds the set of minerals and gases which minimizes the Gibbs free energy of a system with stipulated elemental abundances. Diagrams are presented showing the equilibrium mineralogy, as a function of temperature (400-2300 K), for unfractionated solar material and five fractionated systems. The fractionated systems were defined by mixing, in various proportions, the following four volatility components that solar material can be divided into: refractory dust, carbonaceous matter, ices, and H2 gas. Dust enrichment is seen to increase temperatures of condensation/evaporation and the Fe(2+) content of mafic minerals and to permit existence of stable melt phases. Enrichment of dust and organic matter produces mineral assemblages that are similar in many ways to those of enstatite chondrites, but with mafic minerals that are far more reduced than those in primitive enstatite chondrites. Enrichment of dust, organics, and ices leads to highly ferrous mineralogies even at the highest temperatures but does not predict the stability of hydrous phases above about 450 K.

Wood, John A.↗

Interstellar Dust: Physical Processes

Dust is formed in stellar environments, and destroyed by sputtering, shattering and vaporization in shock waves due to cloud-cloud collisions and supernova blast waves. Dust is also destroyed during star formation. We review the dust formation and destruction balance. The calculated destruction time-scale is less than or equal to one billion years and the star dust injection time-scale is approx. 2.5 billion years. Hence, the fractions of elemental carbon and silicon locked up in stardust are less than 0.3 and less than 0.15, respectively. An efficient ISM dust formation route is therefore implied. In particular, in dense clouds dust grows; through the processes of coagulation and the accretion of gas phase molecules e.g. H20, CO, CH4. These icy materials may then be photoprocessed to refractory materials in more diffuse regions. The resulting carbonaceous grain mantle may actually be the glue that holds the coagulated grains together.

Jones, A. P.↗