Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “carbonaceous materials”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 919 records · Page 51

The Old, Unique C1 Chondrite Flensburg – Insight Into the First Processes of Aqueous Alteration, Brecciation, and the Diversity of Water-Bearing Parent Bodies and Lithologies

On September 12, 2019 at 12:49:48 (UT) a bolide was observed by hundreds of eye-witnesses from the Netherlands, Germany, Belgium, Denmark and the UK. One day later a small meteorite stone was found by accident in Flensburg. The presence of short-lived cosmogenic radionuclides with half-lives as short as 16 days proves the recent exposure of the found object to cosmic rays in space linking it clearly to the bolide event. An exceptionally short exposure time of ∼5000 years was determined. The 24.5 g stone has a fresh black fusion crust, a low density of <2 g/cm(exp 3), and a magnetic susceptibility of logχ = 4.35 (χ in 10−9 m(exp 3)/kg). The rock consists of relict chondrules and clusters of sulfide and magnetite grains set in a fine-grained matrix. The most abundant phases are phyllosilicates. Carbonates (∼3.9 vol.%) occur as calcites, dolomites, and a Na-rich phase. The relict chondrules (often surrounded by sulfide laths) are free of anhydrous silicates and contain abundant serpentine. Lithic clasts are also surrounded by similar sulfide laths partly intergrown with carbonates. Mn-53-Cr-53 ages of carbonates in Flensburg indicate that brecciation and contemporaneous formation of the pyrrhotite-carbonate intergrowths by hydrothermal activities occurred no later than 4564.6 ± 1.0 Ma (using the angrite D'Orbigny as the Mn-Cr age anchor). This corresponds to 2.6 ± 1.0 or 3.4 ± 1.0 Ma after formation of CAIs, depending on the exact absolute age of CAIs. This is the oldest dated evidence for brecciation and carbonate formation, which likely occurred during parent body growth and incipient heating due to decay of Al-26. In the three oxygen isotope diagram, Flensburg plots at the 16O-rich end of the CM chondrite field and in the transition field to CV-CK-CR chondrites. The mass-dependent Te isotopic composition of Flensburg is slightly different from mean CM chondrites and is most similar to those of the ungrouped C2 chondrite Tagish Lake. On the other hand, Ti-50 and Cr-54 isotope anomalies indicate that Flensburg is similar to CM chondrites, as do the ∼10 wt.% H2O of the bulk material. Yet, the bulk Zn, Cu, and Pb concentrations are about 30% lower than those of mean CM chondrites. The He, Ne, and Ar isotopes of Flensburg show no solar wind contribution; its trapped noble gas signature is similar to that of CMs with a slightly lower concentration of Ne(sub tr)-20. Based on the bulk H, C, and N elemental abundances and isotopic compositions, Flensburg is unique among chondrites, because it has the lightest bulk H and N isotopic compositions of any type 1 or 2 chondrite investigated so far. Moreover, the number of soluble organic compounds in Flensburg is even lower than that of the brecciated CI chondrite Orgueil. The extraordinary significance of Flensburg is evident from the observation that it represents the oldest chondrite sample in which the contemporaneous episodes of aqueous alteration and brecciation have been preserved. The characterization of a large variety of carbonaceous chondrites with different alteration histories is important for interpreting returned samples from the OSIRIS-REx and Hayabusa 2 missions.

C1 chondrite↗

Comets, impacts, and atmospheres

Studies of element abundances and values of D/H in the atmospheres of the giant planets and Titan have emphasized the important role of icy planetesimals in the formation of these bodies. In these atmospheres, C/H and D/H increase as the relative masses of the 'cores' of the planets increase. N/H appears to deviate from this trend in an interesting way. In the inner solar system, the traditional approach of using carbonaceous chondrites as the source of planetary volatiles is in serious trouble because of the depletion of xenon and the unusual pattern of xenon isotopes found in the atmospheres of Earth and Mars, and because of the solar-type abundance ratios of argon, krypton and xenon and the large amounts of neon and argon on Venus. Recent studies of elemental abundances in comets, especially P/Halley, coupled with laboratory studies of the trapping of gas in ice formed at low temperatures by A. Bar-Nun et al. provide a consistent interpretation of all of these results. This interpretation emphasizes the fundamental importance of icy planetesimals (comets) and the randomness of early impacts in the formation of planetary systems. Cometary delivery by itself will not explain the noble gas abundances on the inner planets. There is good evidence for at least one additional source, which presumably consists of the rocky material making up the bulk of the planets. The existence of this rocky reservoir is manifested in the nucleogenic isotopes and in the neon which is found in all these atmospheres and is also present in the Earth's mantle. This neon may well be a relic of the planets' earliest, accretional atmospheres.

Owen, Tobias↗

Carbonate compositions in CM and CI chondrites, and implications for aqueous alteration

Carbonate minerals in fourteen CM chondrites and two CI chondrites have been analyzed by electron microprobe to provide a better understanding of the aqueous processes that affected carbonaceous chondrite parent bodies. Calcites in CM chondrites and dolomites and magnesites in CI chondrites display the compositions expected of stable phases formed at low temperatures. Dolomites in CM chondrites, identified here for the first time in five members of the group, have small amounts of excess Ca which may reflect metastable growth. The distribution of Fe between dolomite and coexisting serpentine differs in the two chondrite groups. If the distributions reflect an approach to chemical equilibrium, then the difference implies higher alteration temperatures for the CI group than the CM group in agreement with the results of previously published oxygen isotope thermometry and mineral solubility modeling of the alteration process. Dolomite Fe contents are relatively uniform in the two chondrite groups. Dolomite Mn contents, by contrast, vary widely. The variations may reflect transport-controlled coprecipitation of Mn resulting from a heterogeneous distribution of the element in the anhydrous precursor material. If this interpretation is correct, then the altering fluids were essentially immobile white hydration reactions proceeded on the meteorite parent bodies. The near closed-system character of the alteration process, long known from bulk chemical analyses of the meteorites, is a direct consequence of the limited mobility of dissolved species.

Johnson, Craig A.↗

Sulfur and Oxygen Isotopic Analysis of a Cosmic Symplectite from a Comet Wild 2 Stardust Terminal Particle

Introduction: Analyses of comet 81P/Wild 2 samples re-turned from the Stardust mission have uncovered surprising simi-larities to meteoritic material, including the identification of inner solar system grains [1-3]. The TEM characterization of terminal particle (TP) 4 from Stardust track #147 revealed an assemblage consisting of symplectically intergrown pentlandite and nanocrys-talline maghemite coexisting with high-Ca pyroxene [4]. Mineral-ogically similar cosmic symplectites (COS) containing pentlandite and magnetite in the primitive Acfer 094 meteorite are highly de-pleted in 16O (17O, 18O ~ 180 per mille) [5-7]. This isotopic signature is proposed to record alteration with primordial solar nebula water. Conversely, the normal O isotopic composition of the Stardust COS indicates alteration by a different aqueous reservoir, perhaps on the comet [8]. In this study, we analyzed the Wild 2 COS for S isotopes to further constrain its origin. Experimental: Thin sections of TP4 (12 m) were produced and their mineralogy was thoroughly characterized by TEM. Two of the sections were analyzed for O isotopes by isotopic imaging in the JSC NanoSIMS 50L. The sample in one of the slices was completely consumed. The remaining material in the adjacent slice was analyzed simultaneously for 16O, 32S, 33S, 34S, and 56Fe16O in electron multipliers using a Cs+ primary ion beam. Quasi-simulta-neous arrival (QSA) can have a significant effect on S isotopic ra-tios when using electron multipliers, resulting in undercounting of 32S [9]. Canyon Diablo troilite (CDT) was measured numerous times to deduce a correction factor for QSA and ensure measure-ment reproducibility. Isotopic ratios are reported relative to CDT. Results and Discussion: The Wild 2 COS is enriched in the heavy S isotopes relative to CDT (33S = 6.5 +/- 1.6 per mille; 34S = 5.1 +/- 0.7 per mille; 1). The degree of 33S enrichment indicates mass-inde-pendent fractionation (MIF) with 33S = 3.9 +/- 1.7 per mille. MIF of S has been observed in some chondrules (33S up to 0.11per mille) [10], but this effect has not been identified in sulfides from carbonaceous chondrites [11] or IDPs [12]. S isotopic analysis of Stardust impact craters also did not reveal MIF or anomalies, save for one potential 32S-rich presolar sulfide [13]. Measurement errors on these impact craters were much larger than those in this study, however. MIF of S has been proposed to result from heterogeneities in the solar neb-ula from nucleosynthetic components [14] or photochemical irra-diation of solar nebula gas [10]. Presolar SiC grains are observed to have 32S enrichments [15, 16] contrary to the S isotopic compo-sition of the cometary COS. The S isotopic composition more likely reflects irradiation of nebular gas.

Nguyen, A. N.↗

Enantioselective Three-Dimensional High-Performance Liquid Chromatographic Determination of Amino Acids in the Hayabusa2 Returned Samples from the Asteroid Ryugu

The chirality of amino acids in extraterrestrial materials may provide an insight into the origin of the essential L-enantiopure amino acids in the terrestrial biosphere. In 2020, the Hayabusa2 mission succeeded in bringing back surface materials from the C-type asteroid (162173) Ryugu to the Earth. Amino acids were one of the targeted organic molecules to be studied in the Ryugu samples. To analyze the various structural isomers of amino acids, which were expected to be present, from the limited amount of the returned samples, the development of a highly-sensitive and selective analytical method was necessary. In the present study, a three-dimensional high-performance liquid chromatography (3D-HPLC) system has been developed for the enantioselective determination of five proteinogenic and three non-proteinogenic amino acids in the Ryugu samples, in which amino acids in the sample were separated by reversed-phase, anion-exchange and enantioselective columns after the fluorescence derivatization with 4-fluoro-7-nitro-2,1,3-benzoxadiozole. The applicability of the analytical system to the extraterrestrial samples was evaluated by analyzing several types of carbonaceous meteorites before applying the system to the Ryugu samples. In the analysis of the Ryugu samples, all of the target amino acids were successfully determined quantitatively. Non-proteinogenic amino acids including 2-amino-n-butyric acid, isovaline and norvaline, rarely present in the terrestrial environment, were found as almost racemic mixtures with 47.1 to 55.2%L.

Amino acids↗

The Significance of Slope 1 Variation in Early Solar System Solids

As originally demonstrated by Clayton and co-workers, primitive meteorites and their components commonly display mass-independent oxygen isotopic variation. As a tool to understand this behaviour, a number of reference lines have been defined, with slopes of approximately 1. The Carbonaceous Chondrite Anhydrous Mineral (CCAM) line, derived predominantly from analyses of components in the Allende (CV3) meteorite, is the most widely used reference and has a slope of 0.94 plus or minus 0.01 (2 sigma). However, the fundamental significance of the CCAM line has been questioned. Based on the results of a UV laser ablation study of an Allende CAI (calcium-aluminum–rich inclusion), it was suggested that a line of exactly slope 1 (Y&R line - Young and Russell line) was of more fundamental significance. SIMS (Secondary Ion Mass Spectrometry) analysis of chondrules from primitive CRs and related chondrites define a third, distinct slope 1 line, known as the Primitive Chondrule Minerals (PCM) line. Here we discuss the results of bulk oxygen isotope analysis of CO, CV and CR chondrites and various separated components, with the aim of better understanding the origin of slope 1 behaviour in early Solar System materials.

Greenwood, R. C.↗

Using Neutron Spectroscopy to Constrain the Composition and Provenance of Phobos and Deimos

The origin of the Martian moons Phobos and Deimos is obscure and enigmatic. Hypotheses include the capture of asteroids originally from the outer main belt or beyond, residual material left over from Mars' formation, and accreted ejecta from a large impact on Mars, among others. Measurements of reflectance spectra indicate a similarity to dark, red D-type asteroids, but could indicate a highly space-weathered veneer. Here we suggest a way of constraining the near-surface composition of the two moons, for comparison to known meteoritic compositions. Neutron spectroscopy, particularly the thermal and epithermal neutron flux, distinguishes clearly between various classes of meteorites and varying hydrogen (water) abundances. Perhaps most surprising of all, a rendezvous with Phobos or Deimos is not necessary to achieve this. A low-cost mission based on the LADEE spacecraft design in an eccentric orbit around Mars can encounter Phobos every 2 weeks. As few as five flyby encounters at speeds of 2.3 kilometers per second and closest-approach distance of 3 kilometers provide sufficient data to distinguish between ordinary chondrite, water-bearing carbonaceous chondrite, ureilite, Mars surface, and aubrite compositions. A one-Earth year mission design includes many more flybys at lower speeds and closer approach distances, as well as similar multiple flybys at Deimos in the second mission phase, as described in the Phobos And Deimos Mars Environment (PADME) mission concept. This presentation will describe the expected thermal and epithermal neutron fluxes based on MCNP6 (Monte Carlo N (i.e. Neutron)-Particle transport code (version 6) simulations of different meteorite compositions and their uncertainties.

thtermal and epithermal neutron fluxes↗

CO Chondrite Parent Body Processing as Recorded by Noble Gases

**Introduction:** CO carbonaceous chondrites are among the most primitive meteorites, of which some experienced mild degrees of thermal alteration (up to 500 °C) in their parent asteroid. Previous studies on aqueously altered CM, CY and CR chondrites have shown that the noble gases preserved in those meteorites can be used to assess the extent of parent body processing. This is mostly due to an Ar-rich carrier phase being susceptible to aqueous alteration. In this study, we follow up on these findings by investigating the effects of mild thermal alteration on the noble gas content of CO chondrites. They are subclassified from petrologic subtype 3.0 (e.g., Yamato-81025) to 3.8 (e.g., Isna) according to the degree of thermal alteration experienced. Understanding these effects does not only help to distinguish the most primitive samples from the severely altered ones, but also adds to the picture of the primordial volatile composition and distribution, as preserved in the most primitive material which accreted from the solar nebula at different heliocentric distances. Additionally, we search for pairing among samples, as part of an ongoing survey of Antarctic CO chondrites. **Experimental:** Noble gas measurements were conducted on aliquots of ~20-25 mg from 16 different samples of varying petrologic subtype from 3.0 to 3.8. The gas extraction occurred in one temperature step at ~1700 °C, followed by separation into three fractions, He-Ne, Ar, and Kr-Xe, measured successively in a custom-built mass spectrometer. For each sample, complete gas extraction was verified by a re-extraction step at ~1750 °C. Details on the sample preparation and measurement protocols can be found in. **Results and Discussion:** In most cases, the gas concentrations for all five noble gases decrease with increasing petrologic subtype, and the trend is most pronounced for Ne. An exception is e.g. CO3.0 Colony, which is strongly terrestrially weathered. CO3.8 Isna shows an unusually short expo-sure time to cosmic rays (~0.15 Ma), which may be explained by a direct injection into a mean orbital resonance shortly after collision. The currently ill-defined Ar-rich carrier phase, found only in the least aqueously altered CM and CR samples, is still abundantly present in the predominately anhydrous CO chondrites, indicating that this component is less susceptible to moderately elevated temperatures. No CO chondrites examined so far contain solar wind, supporting the hypothesis that CO chondrites originate from the asteroidal interior. It thus remains enigmatic which material could account for the surface layer.

Noble gas↗

Observation and Analysis of In Situ Carbonaceous Matter in Naklha

The search for indigenous carbon components on Mars has been a challenge. The first attempt was the Viking GC-MS in situ experiment which gave inconclusive results at two sites on Mars [1]. After the discovery that the SNC meteorites were from Mars [2], [3-5] reported C isotopic compositional information which suggested a reduced C component present in the martian meteorites. [6 & 7] reported the presence of reduced C components (i.e., polycyclic aromatic hydrocarbons) associated with the carbonate globules in ALH84001. Jull et al. [8] noted in Nakhla there was an acid insoluble C component present with more than 75% of its C lacking any C-14, which is modern-day carbon. This C fraction was believed to be either indigenous martian or ancient meteoritic carbon. Fisk et al. [9, 10] have shown textural evidence along with C-enriched areas within fractures in Nakhla and ALH84001. To further understand the nature of possible indigenous reduced C components, we have carried out a variety of measurements on martian meteorites. For this presentation we will discuss only the Nakhla results. Interior samples from the Nakhla SNC meteorite, recently made available by the British Museum of Natural History, were analyzed. Petrographic examination [11, McKay et al., this volume] of Nakhla showed evidence of fractures (approx.0.5 micron wide) filled with dark brown to black dendritic material [Fig. 1] with characteristics similar to those observed by [10]. Iddingsite is also present along fractures in olivine. Fracture filling and dendritic material was examined by SEM-EDX, TEM-EDX, Focused Electron Beam microscopy, Laser Raman Spectroscopy, Nano-SIMS Ion Micro-probe, and Stepped-Combustion Static Mass Spectrometry.

Gibson, E. K., Jr.↗

Investigating Combinations of Alkali Metal Oxides and Hydrogenation Catalysts for Reactive Capture of CO2 to Useful C1 Products

As the world endures environmental crises associated with climate change and the rise of atmospheric CO2 concentrations from anthropogenic CO2 emission, carbon capture and utilization (CCU) technologies are increasingly necessary. Reactive carbon capture (RCC) technologies, in which capture and conversion of CO2 occur in a single reactor, are more energetically and economically attractive by avoiding the need to purify, compress, and transport the captured CO2. To this end, dual function materials (DFMs) - composed of sorbents and catalysts co-dispersed on the same high surface area carrier - have been developed. The sorbent component allows for selective capture of CO2 from a gas stream and the catalyst component subsequently performs the in-situ conversion of the adsorbed CO2 upon introduction of a reactive gas (typically H2). The end product of the most established DFM, comprised of Ru and/or Ni with an alkaline sorbent, is methane via the CO2 methanation reaction. While renewable methane would be an excellent transition fuel, fossil methane is inexpensive (averaging $2.57/MMBTU in pre-pandemic 2019) and the economics of renewable methane utilization are noncompetitive. This requires the design and investigation of DFMs that enable CO2 capture and conversion to more valuable and more useful C1 products like CO or methanol (average price of methanol was $20.61/MMBTU in pre-pandemic 2019). These products can then be further upgraded to high energy density synthetic fuels, and related carbonaceous products, for more sustainable alternatives in industries that are difficult to decarbonize, specifically heavy duty vehicles and aviation. Herein, we report various sorbent + catalyst combinations to achieve the production of useful C1 products through reactive capture of CO2.

carbon capture↗

Space-Cabin Atmospheres: Part II - Fire and Blast Hazards. A Literature Review

The rapid evolution of aircraft and, lately, space vehicles has brought with it the ever-increasing difficulty of designing for prevention of fires and explosions. The present-day sealed cabin with its limited work space, unusual atmospheric constituents, and lack of flexibility in emergency situations has brought new and ill-defined hazards into the picture. In the past, numerous data have been compiled on the fire and explosion characteristics of all things combustible. Unfortunately, much of the material is not pertinent to the actual operational problems in space. The confusion and controversy arising from attempts to evaluate the space-cabin fire problem appear to stem from past failure to compile the scattered data and to expose it to critical review and selection. In the compilation that follows, an attempt has been made to review the best available data that was deemed actually pertinent to the present problem. The effects of unusual atmospheres have been emphasized, but, as will soon be evident, other physical parameters also play a major role in determining the nature of the problem. Chapter 1 contains a discussion of pertinent definitions and theory. This is detailed only to the point of anticipating some of the problems of interpretation that may arise in other chapters of the report. Included in this chapter is speculation on the impact of unusual environmental conditions such as aerodynamic heating, reduced gravitational acceleration, and low ambient pressures. Chapter 2 covers flammable fabrics and carbonaceous solids; Chapter 3, specific fire hazards involving flammable liquids, vapors, and gases; and Chapter 4, electrical fires. Chapter 5 covers the fire, blast, and flash hazards from meteoroid penetration; and Chapter 6, the problems of fire prevention and extinguishment in space cabins. Chapter 7 reviews the factors of fire and blast hazards in selection of a space-cabin atmosphere.

Roth, Emanuel M.↗

Light-Hydrocarbon Bearing Solids on Planetesimal 5145 Pholus

Object 5145 Pholus (=1992 AD) is a planetesimal in an orbit that crosses those of Saturn, Uranus, and Neptune (period 92.7 years). It is particularly notable because of its extreme red color, corroborated by several observing teams. A spectrum of Pholus obtained in 1992 shows a strong absorption band with a characteristic shape at 2.27 micrometers, plus a weaker band at 1.7 micrometers. A better spectrum of the 2.0-2.5 micrometer region in 1993 confirms the position and shape of the 2.27-micrometer band. The color and spectral bands are identified with the aliphatic-rich and high H/C organic solid called asphaltite, which in a terrestrial setting originates from thermal processing of products of biological activity. In Pholus, this material is attributed to formation from radiation processing of ices on grains in the interstellar medium. Laboratory spectra of asphaltite and related materials have been published by Moroz et al., while Cloutis showed similar bands in comparable materials and identified them as the overtone and combination bands of C-H stretching and bending modes in CH2 and CH3 groups. Asphaltites, kerites, and anthraxolites are solid non-graphite members of a sequence ranging from oil to graphite; diffuse reflectance spectra of suites of these intermediate materials show color characteristics similar to those of the low-albedo asteroids (C,P,D), although specific identifications have not been made because of the lack of distinct absorption bands in the spectra of most low-albedo solar system bodies. In the case of Pholus, however, the primary band is strong; its wavelength and its shape, plus the match of the extremely red color, leads us to the identification of aliphatic-rich, asphaltite-like organic solid. The C, P, and D-type asteroids vary in degree of "redness", but are all less red than Pholus. Pholus and the Ctype asteroids are the end members of a sequence that represents the radiation processing of hydrocarbons, with Pholus being the least processed. Solar irradiation processes and heating reduce the H/C and aliphatic content of hydrocarbons preserved from the interstellar medium, and in the end produce opaque solids of neutral reflectance, including the kerogens (similar to anthraxolites) found in profusion in the carbonaceous meteorites.

Cruikshank, Dale P.↗

A proposition for the classification of carbonaceous chondritic micrometeorites

Classification of interplanetary dust particles (IDP's) should be unambiguous and, if possible, provide an opportunity to interrelate these ultrafine IDP's with the matrices of undifferentiated meteorites. I prefer a scheme of chemical groupings and petrologic classes that is based on primary IDP properties that can be determined without prejudice by individual investigators. For IDP's of 2-50 microns these properties are bulk elemental chemistry, morphology, shape, and optical properties. The two major chemical groups are readily determined by energy dispersive spectroscopic analysis using the scanning or analytical electron microscope. Refinement of chondritic IDP classification is possible using the dominant mineral species, e.g. olivine, pyroxene, and layer silicates, and is readily inferred from FTIR, and automated chemical analysis. Petrographic analysis of phyllosilicate-rich IDP's will identify smectite-rich and serpentine-rich particles. Chondritic IDP's are also classified according to morphology, viz., CP and CF IDP's are aggregate particles that differ significantly in porosity, while the dense CS IDP's have a smooth surface. The CP IDP's are characterized by an anhydrous silicate mineralogy, but small amounts of layer silicates may be present. Distinction between the CP and CF IDP's is somewhat ambiguous, but the unique CP IDP's are fluffy, or porous, ultrafine-grained aggregates. The CP IDP's, which may contain silicate whiskers, are the most carbon-rich extraterrestrial material presently known. The CF IDP's are much less porous that CP IDP's. Using particle type definitions, CP IDP's in the NASA JSC Cosmic Dust Catalogs are approx. 15 percent of all IDP's that include nonchondritic spheres. Most aggregate particles are of the CF type.

Rietmeijer, Frans J. M.↗

Light-Hydrocarbon Bearing Solids on Planetesimal 5145 Pholus

Object 5145 Pholus (=1992 AD) is a planetesimal in an orbit that crosses those of Saturn, Uranus, and Neptune (period 92.7 years). It is particularly notable because of its extreme red color, corroborated by several observing teams. A spectrum of Pholus obtained in 1992 shows a strong absorption band with a characteristic shape at 2.27 micron, plus a weaker band at 1.7 microns. A better spectrum of the 2.0-2.5 micron region in 1993 confirms the position and shape of the 2.27 micron band. The color and spectral bands are identified with the aliphatic-rich and high H/C organic solid called asphaltite, which in a terrestrial setting originates from thermal processing of products of biological activity. In Pholus, this material is attributed to formation from radiation processing of ices on grains in the interstellar medium. Laboratory spectra of asphaltite and related materials have been published by Moroz et al., while Cloutis showed similar bands in comparable materials and identified them as the overtone and combination bands of C-H stretching and bending modes in CH2 and CH3 groups. Asphaltites, kerites, and anthraxolites are solid non-graphite members of a sequence ranging from oil to graphite; diffuse reflectance spectra of suites of these intermediate materials show color characteristics similar to those of the low-albedo asteroids (C,P,D), although specific identifications have not been made because of the lack of distinct absorption bands in the spectra of most low-albedo solar system bodies. In the case of Pholus, however, the primary band is strong; its wavelength and its shape, plus the match of the extremely red color, leads us to the identification of aliphatic-rich, asphaltite-like organic solid. The C, P, and D-type asteroids vary in degree of 'redness', but are all less red than Pholus. Pholus and the C-type asteroids are the end members of a sequence that represents the radiation processing of hydrocarbons, with Pholus being the least processed. Solar irradiation processes and heating reduce the H/C and aliphatic content of hydrocarbons preserved from the interstellar medium, and in the end produce opaque solids of neutral reflectance, including the kerogens (similar to anthraxolites) found in profusion in the carbonaceous meteorites.

Cruikshank, Dale P.↗

Synthesis of Large Molecules in Cometary Ice Analogs: Physical Properties Related to Self-Assembly Processes

The combination of realistic laboratory simulations and infrared observations have revolutionized our understanding of interstellar dust and ice-the main component of comets. Since comets and carbonaceous micrometeorites may have been important sources of volatiles and carbon compounds on the early Earth, their organic composition may be related to the origin of life. Ices on grains in molecular clouds contain a variety of simple molecules. The D/H ratios of the comets Hale-Bopp and Hyakutake are consistent with a primarily interstellar ice mixture. Within the cloud and especially in the presolar nebula through the early solar system, these icy grains would have been photoprocessed by the ultraviolet producing more complex species such as hexamethylenetetramine, polyoxymethylenes, and simple keones. We reported at the 1999 Bioastronomy meeting laboratory simulations studied to identify the types of molecules which could have been generated in pre-cometary ices. Experiments were conducted by forming a realistic interstellar mixed-molecular ice (H2O, CH3OH, NH3 and CO) at approximately 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The gas mixture was typically 100:50:1:1, however when different ratios were used material with similar characteristics was still produced. The residue that remained after warming to room temperature was analyzed by HPLC, and by several mass spectrometric methods. This material contains a rich mixture of complex compounds with mass spectral profiles resembling those found in IDPs and meteorites. Surface tension measurements show that an amphiphilic component is also present. These species do not appear in various controls or in unphotolyzed samples. Residues from the simulations were also dispersed in aqueous media for microscopy. The organic material forms 10-40 gm diameter droplets that fluoresce at 300-450 nm under UV excitation. These droplets have a morphology and internal structure which appear strikingly similar to those produced by extracts of the Murchison meteorite. Together, these results suggest a link between organic material photochemically synthesized on the cold grains in dense, interstellar molecular clouds and compounds that may have contributed to the organic inventory of the primitive Earth. For example, the amphiphilic properties of such compounds permit self-assembly into the membranous boundary structures that required for the first forms of cellular life.

Dworkin, Jason P.↗

Organics In Meteorites

The variety of classes of organic compounds that occur in carbonaceous meteorites suggests a rich pre-planetary chemistry with possible connections to interstellar, solar nebular and parent body processes. Structural diversity prevails within all classes examined in detail. Among amino acids for instance, all possible isomers are found up to species containing 4-6 carbon atoms, with abundances decreasing with increasing molecular weight. Such diversity seems limited to those carbonaceous meteorites which show evidence of having been exposed to liquid water; meteorites lacking such evidence also show much lower abundances and less structural diversity in their organic contents. This apparent dependency on water suggests a role for cometary ices in the chemical evolution of organic compounds on parent bodies. Measurements of the stable isotope compositions of C, H, N and S in classes of compounds and at the individual compound level show strong deviations from average chondritic values. These deviations are difficult to explain by solar system or parent body processes, and precedents for some of these isotopic anomalies exist in interstellar (e.g., high D/H ratios) and circumstellar chemistry. Therefore, presolar origins for much if not all of the meteoritic organic compounds (or their precursors) is a distinct possibility. In contrast, evidence of solar nebular origins is either lacking or suspect. Results from molecular and isotopic analyses of meteoritic organics, from laboratory simulations and from a model of interstellar grain reactions will be used to flesh out the hypothesis that this material originated with interstellar chemistry, was distributed within the early solar system as cometary ices, and was subsequently altered on meteorite parent bodies to yield the observed compounds.

Chang, Sherwood↗

Tracers of the Extraterrestrial Component in Sediments and Inferences for Earth's Accretion History

The study of extraterrestrial matter in sediments began with the discovery of cosmic spherules during the HMS Challenger Expedition (1873-1876), but has evolved into a multidisciplinary study of the chemical, physical, and isotopic study of sediments. Extraterrestrial matter in sediments comes mainly from dust and large impactors from the asteroid belt and comets. What we know of the nature of these source materials comes from the study of stratospheric dust particles, cosmic spherules, micrometeorites, meteorites, and astronomical observations. The most common chemical tracers of extraterrestrial matter in sediments are the siderophile elements, most commonly iridium and other platinum group elements. Physical tracers include cosmic and impact spherules, Ni-rich spinels, meteorites, fossil meteorites, and ocean-impact melt debris. Three types of isotopic systems have been used to trace extraterrestrial matter. Osmium isotopes cannot distinguish chondritic from mantle sources, but provide a useful tool in modeling long-term accretion rates. Helium isotopes can be used to trace the long-term flux of the fine fraction of the interplanetary dust complex. Chromium isotopes can provide unequivocal evidence of an extraterrestrial source for sediments with high concentrations of meteoritic Cr. The terrestrial history of impacts, as recorded in sediments, is still poorly understood. Helium isotopes, multiple Ir anomalies, spherule beds, and craters all indicate a comet shower in the late Eocene. The Cretaceous-Tertiary boundary impact event appears to have been caused by a single carbonaceous chondrite projectile, most likely of asteroid origin. Little is known of the impact record in sediments from the rest of the Phanerozoic. Several impact deposits are known in the Precambrian, including several possible mega-impacts in the Early Archean.

Kyte, Frank T.↗

Anomalous Role of Carbon in Pd‐Catalyzed Selective Hydrogenation

Carbonaceous species, including subsurface carbidic carbon and surface carbon, play crucial roles in heterogeneous catalysis. Many reports suggested the importance of subsurface carbon in the selective hydrogenation of alkynes over Pd‐based catalysts. However, the role of surface carbon has been largely overlooked. Here, we demonstrate that subsurface carbon in Pd is not responsible for the selectivity in acetylene hydrogenation. In contrast, the structure of surface carbonaceous species plays a decisive role in hydrogenation selectivity. Electron microscopy and spectroscopy evidence, along with theoretical modelling, reveal that partial graphitization of surface carbonaceous species results in unique spatial confinement of surface reaction intermediates, thus altering the reaction energy landscape in favour of ethylene desorption as opposed to over‐hydrogenation. This mechanism for selectivity control is analogous to enzyme catalysis, where the active centers selectively attract reactants and release products. Similar mechanism may be present in CO/CO 2 hydrogenation and alkane dehydrogenation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗