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NASA NTRS2002

Organic Synthesis in Space

This talk will review our current understanding of the synthesis of organic molecules in space, with particular emphasis on the synthesis of those compounds that may be of prebiotic interest. The talk will address the possibility that molecules created in the interstellar medium may play a role in the origin and evolution of life on planetary surfaces. The various organic and volatile compounds that are now known or suspected to exist in a variety of space environments (stellar outflows, the diffuse interstellar medium, dense molecular clouds, protostellar nebulae, and planetesimal parent bodies in planetary systems) will be reviewed. This information comes largely from the combined applications of observational infrared and radio spectroscopy, laboratory astrophysical simulations, and theoretical astrochemistry. This will be followed by a discussion of the evidence, largely gathered from the laboratory isotopic study of extraterrestrial materials (meteorites and cosmic dust), that interstellar materials, including organics, can and do survive the transition from the interstellar space into forming stellar systems. Once there, some of this material can be delivered largely unaltered to planetary surfaces where it can play key roles in the origin and subsequent evolution of life.

Sandford, Scott A.↗

NASA NTRS1999

Mineralogy of the Solar System

The coming decade will witnesses the first sample return missions from solar system bodies in 30 years. These samples will all be very small, some missions return only a few milligrams of total mass. Fortunately, the capability of modem methods to characterize ultra-small samples is well established from analysis of interplanetary dust particles (IDPs), interstellar grains recovered from meteorites, and other materials requiring ultra-sensitive analytical capabilities. Powerful analytical techniques are available that require, under favorable circumstances, single particles of only a few nanograms for entire suites of fairly comprehensive characterizations. A returned sample of greater than 1,000 particles with total mass of just one microgram permits comprehensive quantitative geochemical measurements that are impractical to can-y out in situ by flight instruments. With the Galileo flybys of Gaspra and Ida, it is now recognized that even very small airless bodies have indeed developed a particulate regolith. Acquiring a sample of the bulk regolith, a simple sampling strategy, provides two critical pieces of information about the body. Regolith samples are excellent bulk samples since they normally contain all the key components of the local environment, albeit in particulate form. Furthermore, since this fine fraction dominates remote measurements, regolith samples also provide information about surface alteration processes and are a key link to remote sensing of other bodies. Studies indicate that a statistically significant number of nanogram-sized particles should be able to characterize the regolith of a primitive asteroid, although the presence of larger components within even primitive meteorites (e.g.. Murchison), e.g. chondrules, CAI, large crystal fragments, etc., points out the limitations of using data obtained from nanogram-sized samples to characterize entire primitive asteroids. However, most important asteroidal geological processes have left their mark on the matrix, since this is the finest-grained portion and therefore most sensitive to chemical and physical changes. Thus, the following information can be learned from this fine grain size fraction alone: (1) mineral paragenesis; (2) regolith processes, (3) bulk composition; (4) conditions of thermal and aqueous alteration (if any); (5) relationships to planets, comets, meteorites (via isotopic analyses, including oxygen; (6) abundance of water and hydrated material; (7) abundance of organics; (8) history of volatile mobility, (9) presence and origin of presolar and/or interstellar material.

Zolensky, Michael E.↗

NASA NTRS2013

Micro-ion Traps for Detection of (Pre)-Biotic Organic Compounds on Comets

Comets are currently believed to be a mixture of interstellar and nebular material. Many of the volatiles in comets are attributed to interstellar chemistry, because the same species of carbonaceous compounds are also observed in ices in interstellar molecular (ISM) clouds. Comets are thus likely to be a relatively pristine reservoir of primitive material and carbonaceous compounds in our solar system. They could be a major contributor to the delivery of prebiotic organic compounds, from which life emerged through impacts on early Earth. Mass spectrometers are very powerful tools to identify unknown chemicals, and much progress bas been made in miniaturizing mas spectrometers for space applications. Most miniatu rized mass spectrometers developed to date, however, are still relatively large, power hungry, complicated to assemble, and would have significant impact on space flight vehicle total payload and resource allocations.

vanAmerom, Friso H. W.↗

NASA NTRS2000

Recent Advances in Interstellar Astrochemistry

This presentation will address the possibility that molecules created in the interstellar medium may play a role in the origin and evolution of life on planetary surfaces. The argument will be presented in three main parts. First, I will review the various organic and volatile compounds that are now known or suspected to exist in a variety of circumstellar and interstellar environments. This information is largely the result of the combined applications of observational infrared and radio spectroscopy, laboratory astrophysical simulations, and theoretical astrochemistry. Second, I will devote additional attention to those materials that exhibit chemical properties that are of biological interest. Finally, I will discuss the evidence, largely gathered from the laboratory study of extraterrestrial materials (meteorites and cosmic dust), that interstellar materials, including organics, can survive the transition from the dense cloud phase into forming stellar systems. Once there, some of this material can be delivered largely unaltered to planetary surfaces where it can play key roles in the origin and subsequent evolution of life. Thus, the guiding principle of this presentation will be to attempt to 'put the astro into astrobiology.'

Sandford, Scott A.↗

NASA NTRS1994

Ultraviolet spectra of quenched carbonaceous composite derivatives: Comparison to the '217 nanometer' interstellar absorption feature

QCCs (quenched carbonaceous composite) are amorphus carbonaceous material formed from a hydrocarbon plasma. We present the UV-visible spectra of 'filmy QCC; (obtained outside of the beam ejected from the hydrocarbon plasma) and 'dark QCC' (obtained very near to the beam) for comparison to the stellar extinction curve. When filmy QCC is heated to 500-700 C (thermally altered), the wavelength of the absorption maximum increases form 204 nm to 220-222 nm. The dark QCC has an absorption maximum at 217-222 nm. In addition, the thermally altered filmy QCC has a slope change at about 500 nm which resmbles that in the interstellar extinction curve. The resemblance of the extinction curve of the QCCs to that of the interstellar medium suggests that QCC derivatives may be representative of the type of interstellar material that produces the 217 nm interstellar medium feature. The peak extinction of the dark QCC is higher than the average interstellar extinction curve while that of the thermally altered filmy QCC is lower, so that a mixture of dark and thermally altered filmy QCC can match the peak extinction observed in the interstellar medium. It is shown from electron micrographs that most of the thermally altered flimy QCC is in the form of small grainy structure less than 4 nm in diameter. This shows that the structure unit causing the 217-222 nm feature in QCC is very small.

Sakata, Akira↗

NASA NTRS1976

Secondary cosmic-ray electrons and positrons from 1 to 100 GeV in the upper atmosphere and interstellar space, and interpretation of a recent positron flux measurement

Secondary electron and positron fluxes generated in interstellar space and in the atmosphere from the decays of pions and kaons in inelastic nuclear interactions are calculated by Monte Carlo techniques for lepton energies in the range from 1 to 100 GeV and an assumed thickness of 10 g/sq cm or less for the interstellar or atmospheric material. A simple and accurate analytical model which summarizes the Monte Carlo results and identifies the essential parameters involved is developed and used to interpret a previous positron measurement. It is found that the thickness of interstellar and source material is about 4.3 g/sq cm for cosmic-ray positrons with energies exceeding 4 GeV, a result that is difficult to reconcile with recently proposed two-containment-volume propagation models which predict a thickness of 1.8 g/sq cm for the same energies on the basis of the energy dependence of the measured (Li+Be+B)/(C+O) ratio. It is shown that single-containment-volume (galactic) models invoking an energy-dependent leakage lifetime are compatible with the positron data, but lack a mechanism to explain the energy dependence.

Orth, C. D.↗

NASA NTRS1998

Extraterrestrial organic matter: a review

We review the nature of the widespread organic material present in the Milky Way Galaxy and in the Solar System. Attention is given to the links between these environments and between primitive Solar System objects and the early Earth, indicating the preservation of organic material as an interstellar cloud collapsed to form the Solar System and as the Earth accreted such material from asteroids, comets and interplanetary dust particles. In the interstellar medium of the Milky Way Galaxy more than 100 molecular species, the bulk of them organic, have been securely identified, primarily through spectroscopy at the highest radio frequencies. There is considerable evidence for significantly heavier organic molecules, particularly polycyclic aromatics, although precise identification of individual species has not yet been obtained. The so-called diffuse interstellar bands are probably important in this context. The low temperature kinetics in interstellar clouds leads to very large isotopic fractionation, particularly for hydrogen, and this signature is present in organic components preserved in carbonaceous chondritic meteorites. Outer belt asteroids are the probable parent bodies of the carbonaceous chondrites, which may contain as much as 5% organic material, including a rich variety of amino acids, purines, pyrimidines, and other species of potential prebiotic interest. Richer in volatiles and hence less thermally processed are the comets, whose organic matter is abundant and poorly characterized. Cometary volatiles, observed after sublimation into the coma, include many species also present in the interstellar medium. There is evidence that most of the Earth's volatiles may have been supplied by a 'late' bombardment of comets and carbonaceous meteorites, scattered into the inner Solar System following the formation of the giant planets. How much in the way of intact organic molecules of potential prebiotic interest survived delivery to the Earth has become an increasingly debated topic over the last several years. The principal source for such intact organics was probably accretion of interplanetary dust particles of cometary origin.

NASA Discipline Exobiology↗

NASA NTRS1993

Diamonds in dense molecular clouds - A challenge to the standard interstellar medium paradigm

Observations of a newly discovered infrared C-H stretching band indicate that interstellar diamond-like material appears to be characteristic of dense clouds. In sharp contrast, the spectral signature of dust in the diffuse interstellar medium is dominated by -CH2- and -CH3 groups. This dichotomy in the aliphatic organic component between the dense and diffuse media challenges standard assumptions about the processes occurring in, and interactions between, these two media. The ubiquity of this interstellar diamond-like material rules out models for meteoritic diamond formation in unusual circumstellar environments and implies that the formation of the diamond-like material is associated with common interstellar processes or stellar types.

Allamandola, L. J.↗

NASA NTRS1996

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↗

NASA NTRS2003

Interstellar Deuterium Chemistry

The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer of interstellar components has been deuterium (D) excesses. In some cases these enrichments are seen in bulk meteoritic materials, but D enrichments have also been observed in meteoritic subfractions and even within specific classes of molecular species, such as amino and carboxylic acids. These anomalies are not thought to be the result of nucleosynthetic processes, but are instead ascribed to chemical and physical processes occurring in the interstellar medium (ISM). The traditional explanation of these D excesses has been to invoke the presence of materials made in the ISM by low temperature gas phase ion-molecule reactions. Indeed, the DM ratios seen in the simple interstellar gas phase molecules in cold dense clouds amenable to measurement using radio spectral techniques are generally considerably higher than the values seen in enriched Solar System materials. However, the true linkage between the DM ratios in interstellar and meteoritic materials is obscured by several effects. First, current observations of D enrichment in the ISM have been made of only a few simple molecules, molecules that are not the main carriers of D in Solar System materials. Second, some of the interstellar D enrichment is likely to reside on labile moieties that will have exchanged to some degree with more isotopically normal material during incorporation into the warm protosolar nebula, parent body processing, delivery, recovery, and analysis. Third, ion-molecule reactions represent only one of at least four processes that can produce strong D-H fractionation in the ISM.

Sandford, S. A.↗

NASA NTRS2003

Solar System Connections to the Organic Material In the ISM

The organic component of the interstellar medium (ISM) has relevance to the formation of the early solar nebula, since our solar system formed out of ISM material. Comparisons of near infrared spectra of the diffuse ISM dust with those of primitive solar system bodies (such as comets and meteorites) show a remarkable similarity, suggesting that perhaps some of the interstellar organic material made its way, unaltered, into our solar system. Tracing the interstellar organic material is necessary to understand how these materials may be important links in the development of prebiotic phenomena. Studies of the ISM reveal that the organic refractory component of the diffuse ISM is largely hydrocarbon in nature, possessing little N or O, with carbon distributed between the aromatic and aliphatic forms. There is a strong similarity in the near IR spectra of the diffuse ISM (the 3.4 micron hydrocarbon bands) and those seen in the Murchison and Orgueil meteorites, however, detailed comparisons at longer wavelengths reveal critical dissimilarities. Here we will present comparisons and discussion of relevant spectra. As we continue to explore, we will gain insight into the connection between planetesimals in the solar system and chemistry in the dusty space between the stars.

Pendleton, Yvonne J.↗

NASA NTRS1985

Short-lived nuclei in the early solar system

An overview is given of the existence and abundance of short-lived nuclei that were present in the early solar system. It is shown that there are excesses of certain isotopes that may be assigned to the decay of short-lived radioactive nuclei corresponding to an abundance of about 0.0001 relative to a neighboring stable isotope. This abundance is roughly similar to the level of general nonlinear isotopic anomalies present in meteoritic material (excluding oxygen) which are not attributable to short-lived nuclei. If these results are representative of the bulk solar system, they indicate that about 0.0001 solar mass of freshly synthesized material of peculiar composition was added to the protosolar nebula as it was formed from the interstellar medium. This material must have been synthesized about three million yr before the formation of the solar system.

Wasserburg, G. J.↗

NASA NTRS2000

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

NASA Center ARC↗

NASA NTRS2003

Complex Organics from Laboratory Simulated Interstellar Ices

Many of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. The low temperatures of these ices (T < 50 K) preclude most chemical reactions, but photolysis can drive reactions that produce a suite of new species, many of which are complex organics. We study the UV and proton radiation processing of interstellar ice analogs to explore links between interstellar chemistry, the organics in comets and meteorites, and the origin of life on Earth. The high D/H ratios in some interstellar species, and the knowledge that many of the organics in primitive meteorites are D-enriched, suggest that such links are plausible. Once identified, these species may serve as markers of interstellar heritage of cometary dust and meteorites. Of particular interest are our findings that UV photolysis of interstellar ice analogs produce molecules of importance in current living organisms, including quinones, amphiphiles, and amino acids. Quinones are essential in vital metabolic roles such as electron transport. Studies show that quinones should be made wherever polycyclic aromatic hydrocarbons are photolyzed in interstellar ices. In the case of anthracene-containing ices, we have observed the production of 9-anthrone and 9,10 anthraquinone, both of which have been observed in the Murchison meteorite. Amphiphiles are also made when mixed molecular ices are photolyzed. These amphiphiles self-assemble into fluorescent vesicles when placed in liquid water, as do Murchison extracts. Both have the ability to trap an ionic dye. Photolysis of plausible ices can also produce alanine, serine, and glycine as well as a number of small alcohols and amines. Flash heating of the room temperature residue generated by such experiments generates mass spectral distributions similar to those of IDPs. The detection of high D/H ratios in some interstellar molecular species, and the knowledge that many of the organics, such as hydroxy and amino acids, in primitive meteorites are D-enriched provides evidence for a connection between intact organic material in the interstellar medium and in meteorites. Thus, some of the oxidized aromatics, amphiphiles, amino acids, hydroxy acids, and other compounds found in meteorites may have had an interstellar ancestry and not solely a product of parent body aqueous alteration. Such compounds should also be targeted for searches of organics in cometary dust.

Dworkin, J. P.↗

NASA NTRS2003

Simulation of Prebiotic Processing by Comet and Meteoroid Impact: Implications for Life on Early Earth and Other Planets

We develop a reacting flow model to simulate the shock induced chemistry of comets and meteoroids entering planetary atmospheres. Various atmospheric compositions comprising of simpler molecules (i.e., CH4, CO2, H2O, etc.) are investigated to determine the production efficiency of more complex prebiotic molecules as a function of composition, pressure, and entry velocity. The possible role of comets and meteoroids in creating the inventory of prebiotic material necessary for life on Early Earth is considered. Comets and meteoroids can also introduce new materials from the Interstellar Medium (ISM) to planetary atmospheres. The ablation of water from comets, introducing the element oxygen into Titan's atmosphere will also be considered and its implications for the formation of organic and prebiotic material.

Dateo, Christopher E.↗

NASA NTRS2012

Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde

Primitive Solar System materials (e.g. chondrites. IDPs, the Stardust sample) show large variations in isotopic composition of the major volatiles (H, C, N, and O ) even within samples, witnessing to various degrees of processing in the protosolar nebula. For ex~ ample. the very pronounced D enhancements observed in IDPs [I] . are only generated in the cold. dense component of the interstellar medium (ISM), or protoplanetary disks, through ion-molecule reactions in the presence of interstellar dust. If this isotopic anomaly has an interstellar origin, this leaves open the possibility for preservation of other isotopic signatures throughout the form ation of the Solar System. The most common form of carbon in the ISM is CO molecules, and there are two potential sources of C-13 fractionation in this reservoir: low temperature chemistry and selective photodissociation. While gas-phase chemistry in cold interstellar clouds preferentially incorporates C-13 into CO [2], the effect of self-shielding in the presence of UV radiation instead leads to a relative enhancement of the more abundant isotopologue, 12CO. Solar System organic material exhibit rather small fluctuations in delta C-13 as compared to delta N-15 and delta D [3][1], the reason for which is still unclear. However, the fact that both C-13 depleted and enhanced material exists could indicate an interstellar origin where the two fractionation processes have both played a part. Formaldehyde (H2CO) is observed in the gas-phase in a wide range of interstellar environments, as well as in cometary comae. It is proposed as an important reactant in the formation of more complex organic molecules in the heated environments around young stars, and formaldehyde polymers have been suggested as the common origin of chondritic insoluable organic matter (IOM) and cometary refractory organic solids [4]. The relatively high gas-phase abundance of H2CO observed in molecular clouds (10(exp- 9) - 10(exp- 8) relative to H2) makes it feasible to observe its less common isotopologues. As a step in our investigation of C-13 fractionation patterns in the ISM, we here present comparisons between observations of the C-13 fraction in formaldehyde, and chemical fractionation models.

Wirstrom, E. S.↗

NASA NTRS1994

Carbonaceous Components in the Comet Halley Dust

Cometary grains containing large amounts of carbon and/or organic matter (CHON) were discovered by in situ measurements of comet Halley dust composition during VEGA and GIOTTO flyby missions. In this paper, we report the classification of these cometary, grains by means of cluster analysis, discuss the resulting compositional groups, and compare them with substances observed or hypothesized in meteorites, interplanetary dust particles, and the interstellar medium. Grains dominated by carbon and/or organic matter (CHON grains) represent approx. 22% of the total population of measured cometary dust particles. They, usually contain a minor abundance of rock-forming elements as well. Grains having organic material are relatively more abundant in the vicinity of the nucleus than in the outer regions of the coma, which suggests decomposition of the organics in the coma environment. The majority of comet Halley organic particles are multicomponent mixtures of carbon phases and organic compounds. Possibly, the cometary CHON grains may be related to kerogen material of an interstellar origin in carbonaceous meteorites. Pure carbon grains, hydrocarbons and polymers of cyanopolyynes, and multi-carbon monoxides are present in cometary dust as compositionally simple and distinctive components among a variety of others. There is no clear evidence of significant presence of pure formaldehyde or HCN polymers in Halley dust particles. The diversity of types of cometary organic compounds is consistent with the inter-stellar dust model of comets and probably reflects differences in composition of precursor dust. Preservation of this heterogeneity among submicron particles suggest the gentle formation of cometary, nucleus by aggregation of interstellar dust in the protosolar nebula without complete mixing or chemical homogenization at the submicron level.

Fomenkova, M. N.↗

NASA NTRS1993

Main-sequence stars with circumstellar solid material - The Vega phenomenon

The detection of solid grains with temperatures of 50 to 125 K and fractional bolometric luminosities in the range 10 exp -5 to 10 exp -3 early in the IRAS mission around three nearby A main-sequence stars, Alpha Lyrae (Vega), Alpha Piscis Austrinus (Fomalhaut), and Beta Pictoris, is discussed. Spatial resolution of the emission indicates that: the grains are larger than interstellar grains, the material probably lies in disks in the stellar equatorial planes, the disks extend to distances of 100 to 1000 AU from the stars, and zones a few tens of AU in radius around the central stars are relatively empty. Subsequent surveys of IRAS data reveal more than 100 main-sequence stars of all spectral classes having unresolved excesses with similar temperatures and fractional luminosities to the three prototypes. Some stars with excesses have estimated ages of 1 to 5 Gyr. Thus, main-sequence FIR excesses appear to be widespread and are present in systems old enough to be probably past the stage of active planet formation.

Backman, Dana E.↗