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All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

PHYS: Division of Physical Chemistry 258 - Properties and Origins of Cometary and Asteroidal Organic Matter Delivered to the Early Earth

Comets and asteroids may have contributed much of the Earth's water and organic matter. The Earth accretes approximately 4x10(exp 7) Kg of dust and meteorites from these sources every year. The least altered meteorites contain complex assemblages of organic compounds and abundant hydrated minerals. These carbonaceous chondrite meteorites probably derive from asteroids that underwent hydrothermal processing within the first few million years after their accretion. Meteorite organics show isotopic and chemical signatures of low-T ion-molecule and grain-surface chemistry and photolysis of icy grains that occurred in cold molecular clouds and the outer protoplanetary disk. These signatures have been overprinted by aqueously mediated chemistry in asteroid parent bodies, forming amino acids and other prebiotic molecules. Comets are much richer in organic matter but it is less well characterized. Comet dust collected in the stratosphere shows larger H and N isotopic anomalies than most meteorites, suggesting better preservation of primordial organics. Rosetta studies of comet 67P coma dust find complex organic matter that may be related to the macromolecular material that dominates the organic inventory of primitive meteorites. The exogenous organic material accreting on Earth throughout its history is made up of thousands of molecular species formed in diverse processes ranging from circumstellar outflows to chemistry at near absolute zero in dark cloud cores and the formative environment within minor planets. NASA and JAXA are currently flying sample return missions to primitive, potentially organic-rich asteroids. The OSIRIS-REx and Hayabusa2 missions will map their target asteroids, Bennu and Ryugu, in detail and return regolith samples to Earth. Laboratory analyses of these pristine asteroid samples will provide unprecedented views of asteroidal organic matter relatively free of terrestrial contamination within well determined geological context. Studies of extraterrestrial materials and returned samples are essential to understand the origins of Solar System organic material and the roles of comets and asteroids to providing the starting materials for the emergence of life.

Messenger, Scott↗
DOE OSTI2021

Spectroscopic Investigation of the High-Pressure Behavior of Aliphatic Hydrocarbon: Implications for Planetary Processes

Octadecane (C 18 H 38 ) is an aliphatic hydrocarbon that is abundant in carbonaceous chondritic meteorites. It is debated whether these hydrocarbons found in the meteorite are pristine or are a result of subsequent modifications as these meteorites are delivered to the Earth. It is well-known that meteorites are often subjected to extreme pressures and temperatures upon entering the Earth’s atmosphere. To explore the behavior of octadecane at high pressures, that is, how its molecular structure responds to compression, we use a diamond anvil cell in conjunction with Raman spectroscopy. Here, we find that at room temperatures, upon compression to ~5 GPa, a linear-chain octadecane molecule transforms into a bent-chain configuration. Similar transitions from linear to a bent configuration in other hydrocarbons have been documented. We find a linear correlation between the transition pressure from linear to bent configuration, and the chain length of the alkane, that is, longer chain lengths, is likely to be less stable in the linear configuration under compression. These kinks in the bent-chain configuration are likely sites for the dissociation of the longer chain hydrocarbons to smaller hydrocarbons. The octadecane sample examined in this study did not undergo any additional transition to the highest pressure (~18 GPa) explored in this study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Isotopically distinct reservoirs in the solar nebula: Isotope anomalies in Vigarano meteorite inclusions

The isotopic compositions of Mg, Ca, Ti, Cr, Zn, Sr, Ba, Nd, and Sm were measured in four relatively unaltered refractory inclusions from the Vigarano carbonaceous chondrite meteorite. Three of the inclusions (USNM 1623-2, 1623-3, and 1623-8) show similar Mg, Ca, Ti, and Cr isotopic compositions to those found in most inclusions in the Allende carbonaceous chondrite. This indicates that these Vigarano inclusions sampled the same isotopic reservoirs as the majority of the Allende inclusions that isotope signatures in the latter were not significantly modified by the secondary alteration that permeates most Allende inclusions. In contrast, inclusion 1623-5 has large deficits in Mg-26, Ca-48, and Ti-50 and small but distinct Cr-54, Zn-66, Sr-84, Ba-135, Ba-137, and Sm-144 anomalies. The magnitudes of these unusual anomalies in the refractory elements are within analytical uncertainty of those found in the Allende 'FUN" inclusion C1, yet 1623-5 has a very different bulk chemical composition from C1. The fact that 1623-5 and C1 have identical isotopic anomalies yet have significantly distinct major and trace element contents provide convincing evidence for the presence of isotopically distinct reservoirs in the early solar system.

Loss, R. D.↗
NASA NTRS2017

Pathways to Meteoritic Glycine and Methylamine

Glycine and methylamine are meteoritic water-soluble organic compounds that provide insights into the processes that occurred before, during, and after the formation of the Solar System. Both glycine and methylamine and many of their potential synthetic precursors have been studied in astrophysical environments via observations, laboratory experiments, and modeling. Despite these studies, the synthetic mechanisms for their formation leading to their occurrence in meteorites remain poorly understood. Typical 13C-isotopic values ((delta)13C) of meteoritic glycine and methylamine are 13C-enriched relative to their terrestrial counterparts; thus, analyses of their stable carbon isotopic compositions (13C/12C) may be used not only to assess terrestrial contamination in meteorites but also to provide information about their synthetic routes inside the parent body. Here, we examine potential synthetic routes of glycine and methylamine from a common set of precursors present in carbonaceous chondrite meteorites, using data from laboratory analyses of the well-studied CM2 Murchison meteorite. Several synthetic mechanisms for the origins of glycine and methylamine found in carbonaceous chondrites may be possible, and the prevalence of these mechanisms will largely depend on (a) the molecular abundance of the precursor molecules and (b) the levels of processing (aqueous and thermal) that occurred inside the parent body. In this work, we also aim to contextualize the current knowledge about gas-phase reactions and irradiated ice grain chemistry for the synthesis of these species through parent body processes. Our evaluation of various mechanisms for the origins of meteoritic glycine and methylamine from simple species shows what work is still needed to evaluate both the abundances and isotopic compositions of simpler precursor molecules from carbonaceous chondrites as well as the effects of parent body processes on those abundances and isotopic compositions. The analyses presented here combined with the indicated measurements will aid a better interpretation of quantitative analysis of reaction rates, molecular stability, and distribution of organic products from laboratory simulations of interstellar ices, astronomical observations, and theoretical modeling.

interstellar ice↗
NASA NTRS2011

Distinct Purine Distribution in Carbonaceous Chondrites

Carbonaceous chondrite meteorites are known to contain a diverse suite of organic compounds, many of which are essential components of biochemistry. Amino acids, which are the monomers of proteins, have been extensively studied in such meteorites (e.g. Botta and Bada 2002; Pizzarello et aI., 2006). The origin of amino acids in meteorites has been firmly established as extraterrestrial based on their detection typically as racemic mixtures of amino acids, the presence of many non-protein amino acids, and non-terrestrial values for compound-specific deuterium, carbon, and nitrogen isotopic measurements. In contrast to amino acids, nucleobases in meteorites have been far less studied. Nucleobases are substituted one-ring (pyrimidine) or two-ring (purine) nitrogen heterocyclic compounds and serve as the information carriers of nucleic acids and in numerous coenzymes. All of the purines (adenine, guanine, hypoxanthine, and xanthine) and pyrimidines (uracil) previously reported in meteorites are biologically common and could be interpreted as the result of terrestrial contamination (e.g. van del' Velden and Schwartz, 1974.) Unlike other meteoritic organics, there have been no observations of stochastic molecular diversity of purines and pyrimidines in meteorites, which has been a criterion for establishing extraterrestrial origin. Maltins et al. (2008) performed compound-specific stable carbon isotope measurements for uracil and xanthine in the Murchison meteorite. They assigned a non-terrestrial origin for these nucleobases; however, the possibility that interfering indigenous molecules (e.g. carboxylic acids) contributed to the 13C-enriched isotope values for these nucleobases cannot be completely ruled out. Thus, the origin of these meteoritic nucleobases has never been established unequivocally. Here we report on our investigation of extracts of II different carbonaceous chondrites covering various petrographic types (Cl, CM, and CR) and degrees of aqueous alteration (l, 2, and 3) and one ureilite. Analysis via liquid chromatography coupled with electrospray triple-stage mass spectrometry or orbitrap mass spectrometry employed a targeted approach for analysis focused on the five canonical RNA/DNA nucleobases as well as 14 non-canonical pyrimidines and purines, which have bcen observed under plausible prebiotic reactions.

Callahan, Michael P.↗
NASA NTRS2014

Aqueous Alteration of Enstatite Chondrites

The Kaidun meteorite is different from all other meteorites [1], consisting largely of a mixture of “incompatible” types of meteoritic material – carbonaceous and enstatite chondrites, i.e. corre-sponding to the most oxidized and the most reduced samples of meteorite materials, including CI1, CM1-2, CV3, EH3-5, and EL3. In addition to these, minor amounts of ordinary and R chondrites are present. In addition, approximately half of the Kaidun lithologies are new materials not known as separate meteorites. Among these are aqueously altered enstatite chondrites [1], which are of considerable interest because they testify that not all reduced asteroids escaped late-stage oxidation, and hydrolysis, and also because hydrated poorly crystalline Si-Fe phase, which in turn is re-placed by serpentine (Figs 3-5). In the end the only indication of the original presence of metal is the re-sidual carbides. In other enstatite chondrite lithogies (of uncertain type) original silicates and metal have been thoroughly replaced by an assemblage of authi-genic plagioclase laths, calcite boxwork, and occasion-al residual grains of silica, Cr-rich troilite, ilmenite, and rare sulfides including heideite (Fig. 6). Fe and S have been largely leached from the rock (Fig. 4). Again the accessory phases are the first clue to the original character of the rock, which can be verified by O isotopes. It is fortunate that Kaidun displays every step of the alteration process.

Zolensky, M. E.↗
NASA NTRS1979

Ion-beam analysis of meteoritic and lunar samples

Charged particle-induced nuclear reactions were used in the following problems: the determination of elemental abundances of boron and fluorine in carbonaceous chondritic meteorites; the identification of products of lunar vulcanism; and the study of solar wind-implanted atoms in lunar materials. The technique was seen as an important supplement to other methods of elemental and isotopic analysis. This was especially true for cases involving light elements at very low concentrations or where high resolution depth distribution information was needed in non-destructive analysis.

Tombrello, T. A.↗
NASA NTRS2016

Indigenous Carbonaceous Matter in the Nakhla Mars Meteorite

Detailed microanalysis of the Martian meteorite Nakhla has shown there are morphologically distinct carbonaceous features spatially associated with low-T aqueous alteration phases including salts and id-dingsite. A comprehensive suite of analytical instrumentation including optical microscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, focused ion beam (FIB) microscopy, transmission electron microscopy (TEM), two-step laser mass spectrometry (mu-L(sup 2)MS), laser mu-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and nanoscale secondary ion mass spectrometry (NanoSIMS) are being used to characterize the carbonaceous matter and host mineralogy. The search for carbonaceous matter on Mars has proved challenging. Viking Landers failed to unambiguously detect simple organics at either of the two landing sites although the Martian surface is estimated to have acquired at least 10(exp15) kg of C as a consequence of meteoritic accretion over the last several Ga. The dearth of organics at the Martian surface has been attributed to various oxidative processes including UV photolysis and peroxide activity. Consequently, investigations of Martian organics need to be focused on the sub-surface regolith where such surface processes are either severely attenuated or absent. Fortuitously since Martian meteorites are derived from buried regolith materials they provide a unique opportunity to study Martian organic geochemistry.

Clemett, S. J.↗
NASA NTRS1986

Electrical conductivity of carbonaceous chondrites and electric heating of meteorite parent bodies

The electrical conductivity of samples of the Murchison and Allende carbonaceous chondrites is 4 to 6 magnitudes greater than rock forming minerals such as Olivine up to 700 C. The remarkably high electrical conductivity of these meteorites is attributed to carbon at grain boundaries. The environment in the wake of the space station can be exploited to produce conditions which will allow pyrolysis of carbonaceous chondrites. An experimental package consisting of a one square meter shield attached to a 15 cm diameter by 40 cm long furnace and tied to a conductance bridge, furnace controller, and digital voltmeter inside the space station via umbilical cable could make the required measurements. Since heating rates as low as 0.1 C/hour are required to study kinetics of the pyrolysis reations which are the cause of the high conductivity of the carbonaceous chondrites, experimental times up to 3 months will be needed.

Duba, A.↗
NASA NTRS2011

Asteroid (101955) 1999 RQ36: Spectroscopy from 0.4 to 2.4 Micrometer and Meteorite Analogs

We present reflectance spectra from 0.4 to 2.4 ?m of Asteroid (101955) 1999 RQ36, the target of the OSIRIS-REx spacecraft mission. The visible spectral data were obtained at the McDonald Observatory 2.1-m telescope with the ES2 spectrograph. The infrared spectral data were obtained at the NASA Infrared Telescope Facility using the SpeX instrument. The average visible spectrum is combined with the average near-infrared wavelength spectrum to form a composite spectrum. We use three methods to constrain the compositional information in the composite spectrum of Asteroid (101955) 1999 RQ36 (hereafter RQ36). First, we perform a least-squares search for meteorite spectral analogs using 15,000 spectra from the RELAB database. Three most likely meteorite analogs are proposed based on the least-squares search. Next, six spectral parameters are measured for RQ36 and their values are compared with the ranges in parameter values of the carbonaceous chondrite meteorite classes. A most likely meteorite analog group is proposed based on the depth of overlap in parameter values. The results of the least-squares search and the parametric comparisons point to CIs and/or CMs as the most likely meteorite analogs for RQ36, and COs and CHs as the least likely. RQ36 has a spectrally blue continuum slope that is also observed in carbonaceous chondrites containing magnetite. We speculate that RQ36 is composed of a CM1 -like material. Finally, we compare RQ36 to other B-type asteroids measured by Clark et al. (Clark, B.E. et al. [2010]. J. Geophys. Res. 115, E06005). The results of this comparison are inconclusive. RQ36 is comparable to Themis spectral properties in terms of its albedo, visible spectrum, and near-infrared spectrum from 1.1 to 1.45 micrometers. However, RQ36 is more similar to Pallas in terms of its near-infrared spectrum from 1.6 to 2.3 micrometers. Thus it is possible that B-type asteroids form a spectral continuum and that RQ36 is a transitional object, spectrally intermediate between the two end-members. This is particularly interesting because Asteroid 24 Themis was recently discovered to have H2O ice on the surface (Rivkin, A., Emery, J. [2010]. Nature 464, 1322 1323; Campins, H. et al. [2010a]. Nature 464, 1320 1321).

Clark, Beth Ellen↗
NASA NTRS1989

Abundances of volatile-bearing phases in carbonaceous chondrites and cooling rates of meteorites based on cation ordering of orthopyroxenes

Results of preliminary calculations of volatile abundances in carbonaceous chondrites are discussed. The method (Ganguly 1982) was refined for the calculation of cooling rate on the basis of cation ordering in orthopyroxenes, and it was applied to the derivation of cooling rates of some stony meteorites. Evaluation of cooling rate is important to the analysis of condensation, accretion, and post-accretionary metamorphic histories of meteorites. The method of orthopyroxene speedometry is widely applicable to meteorites and would be very useful in the understanding of the evolutionary histories of carbonaceous chondrites, especially since the conventional metallographic and fission track methods yield widely different results in many cases. Abstracts are given which summarize the major conclusions of the volatile abundance and cooling rate calculations.

Ganguly, Jibamitra↗