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NASA NTRS2000

Laboratory Astrochemistry: Interstellar PAH Analogs

Polycyclic aromatic hydrocarbons (PAHs) are now considered to be an important and ubiquitous component of the organic material in space. PAHs are found in a large variety of extraterrestrial materials such as interplanetary dust particles (IDPs) and meteoritic materials. PAHs are also good candidates to account for the infrared emission bands (UIRs) and the diffuse interstellar optical absorption bands (DIBs) detected in various regions of the interstellar medium. The recent observations made with the Infrared Space Observatory (ISO) have confirmed the ubiquitous nature of the UIR bands and their carriers. PAHs are though to form through chemical reactions in the outflow from carbon-rich stars in a process similar to soot formation. Once injected in the interstellar medium, PAHs are further processed by the interstellar radiation field, interstellar shocks and energetic particles. A major, dedicated, laboratory effort has been undertaken over the past years to measure the physical and chemical characteristics of these complex molecules and their ions under experimental conditions that mimic the interstellar conditions. These measurements require collision-free conditions where the molecules and ions are cold and chemically isolated. The spectroscopy of PAHs under controlled conditions represents an essential diagnostic tool to study the evolution of extraterrestrial PAHs. The Astrochemistry Laboratory program will be discussed through its multiple aspects: objectives, approach and techniques adopted, adaptability to the nature of the problem(s), results and implications for astronomy as well as for molecular spectroscopy. A review of the data generated through laboratory simulations of space environments and the role these data have played in our current understanding of the properties of interstellar PAHs will be presented. The discussion will also introduce the newest generation of laboratory experiments that are currently being developed in order to provide a closer simulation of space environments and a better support to space missions.

Salama, Farid↗

NASA NTRS2000

Laboratory Studies of Interstellar PAH Analogs

Salama, Farid↗

NASA NTRS2010

VAPoR - Volatile Analysis by Pyrolysis of Regolith - an Instrument for In Situ Detection of Water, Noble Gases, and Organics on the Moon

We present the Volatile Analysis by Pyrolysis of Regolith (VAPoR) instrument design and demonstrate the validity of an in situ pyrolysis mass spectrometer for evolved gas analyses of lunar and planetary regolith samples. In situ evolved gas analyses of the lunar regolith have not yet been carried out and no atmospheric or evolved gas measurements have been made at the lunar poles. VAPoR is designed to do both kinds of measurements, is currently under development at NASA's Goddard Space Flight Center, and will be able to heat powdered regolith samples or rock drill fines up to 1400 C in vacuo. To validate the instrument concept, evolved gas species released from different planetary analogs were determined as a function of temperature using a laboratory breadboard. Evolved gas measurements of an Apollo 16 regolith sample and a fragment of the carbonaceous meteorite Murchison were made by VAPoR and our results compared with existing data. The results imply that in situ evolved gas measurements of the lunar regolith at the polar regions by VAPoR will be a very powerful tool for identifying water and other volatile signatures of lunar or exogenous origin as potential resources for future human exploration.

ten Kate, I. L.↗

NASA NTRS2002

Carbonate Globules in Columbia River Basalt The Search for Life in Terrestrial Subsurface Environments as Possible Martian Analogs

Basalts from the Columbia River (CRB) Plateau contain minor amounts of carbonates of unknown origins. We have examined the petrology and chemistry of the CRB carbonates to elucidate the modes of formation. This study is directly relevant to meteorites and future samples returned from Mars. Additional information is contained in the original extended abstract.

Starke, V.↗

NASA NTRS1976

Volatile inventories on Mars

Predictions for the total inventory of outgassed volatiles on Mars can be developed by studying volatiles in meteorites, terrestrial rocks, and the atmospheres of Venus, the moon, and the earth. Two models are presented, following the basic assumption that the devolatilization of Mars has been analogous to that of the earth. The recent discovery of a high abundance of argon in the Martian atmosphere appears to indicate that Mars has outgassed as completely as the earth, but present uncertainties and lacunae in the essential data set permit several other interpretations.

Owen, T.↗

NASA NTRS1998

Biomarkers in Carbonate Thermal Springs: Implications for Mars

Evidence of possible relict biogenic activity has been reported in carbonate inclusions within martian meteorite ALH 84001. The initial evidence included ovoid and elongated forms 50 - 500 nanometers in length, morphologically similar to but significantly smaller than many terrestrial microbes. More recently, thin structures resembling the remains of organic biofilms have been reported in the same meteorite. Carbonates have also been discussed in the context of Mars sample return missions. Thermal spring deposits have often been cited as prime locations for exobiological exploration. By analogy to Earth, specialized microbes may have existed in the heated, mineralized waters, and precipitates of carbonate and/or silica from these waters may have trapped and preserved evidence of life. Since the geological interactions that produce thermal springs can be recognized in orbital imagery, directed searches for microfossils in such deposits are deemed possible. We are engaged in a study of the signatures produced by contemporary biogenic activity (biomarkers) in carbonate thermal springs. We are examining the microbes that live in such environments and the preservation of microbial forms, biofilms, and petrographic fabrics indicative of life in thermal spring mineral deposits. This work is part of a much more extensive study to refine the appropriate tools, techniques, and approaches to seek evidence of life in a range of planetary samples. A deeper understanding of biological signatures will prepare us for the detailed search for life on Mars and eventually on other planets. Overall. the study of biomarkers in rocks and soils will provide insight into the evolution of life because such signatures are a record of how life interacts with its environment, how it adapts to changing conditions, and how life can influence geology and climate.

Allen, C. C.↗

NASA NTRS2014

Astromaterials Research Office (KR) Overview

The fundamental goal of our research is to understand the origin and evolution of the solar system, particularly the terrestrial, "rocky" bodies. Our research involves analysis of, and experiments on, astromaterials in order to understand their nature, sources, and processes of formation. Our state-of-the-art analytical laboratories include four electron microbeam laboratories for mineral analysis, four spectroscopy laboratories for chemical and mineralogical analysis, and four mass spectrometry laboratories for isotopic analysis. Other facilities include the experimental impact laboratory and both 1-atm gas mixing and high-pressure experimental petrology laboratories. Recent research has emphasized a diverse range of topics, including: Study of the solar system's primitive materials, such as carbonaceous chondrites and interplanetary dust; Study of early solar system chronology using short-lived radioisotopes and early nebular processes through detailed geochemical and isotopic characterizations; Study of large-scale planetary differentiation and evolution via siderophile and incompatible trace element partitioning, magma ocean crystallization simulations, and isotopic systematics; Study of the petrogenesis of Martian meteorites through petrographic, isotopic, chemical, and experimental melting and crystallization studies; Interpretation of remote sensing data, especially from current robotic lunar and Mars missions, and study of terrestrial analog materials; Study of the role of organic geochemical processes in the evolution of astromaterials and the extent to which they constrain the potential for habitability and the origin of life.

Draper, David S.↗

NASA NTRSDate not supplied

Exploration of A Magma-Sediment Hydrothermal System on Earth: Constraints on the Habitability Potential of Martian Noachian Hydrothermal Systems

The martian crust is predominantly composed of basalt [1] and hosts a large variety of alteration materials caused by wide-ranging processes from volcanic hydrothermal processes to sedimentary and post-magmatic (e.g., see [2] and reference within). Specifically, there is an abundance of evidence that water previously flowed on Mars, ranging from ancient stream beds [3], lake basins [4], sedimentary fans in Jezero crater [5, 6], and clay minerals [7]. These secondary minerals have been observed by landers and rovers [2], from orbit [8], and in martian meteorites [9-11]. Along with low temperature alteration, high temperature hydrothermal systems from volcanic processes, as well as meteorite impacts, should have been present [12,13]. However, finding evidence of high-temperature hydrothermal activity has been challenging. To better understand these processes on Mars, Earth analogs can be used and then compared to potential scenarios and locations on Mars. Therefore, here we investigate a mafic dike and the surrounding metamorphic contact zone that has been hydrothermally altered from contact with ground water as it was emplaced. We will also compare our results to previous work on Robbers Roost Dike, an older mafic dike near our field location that intruded a similar protolith causing a potentially habitable hydrothermal system [14. 15].

R A Slank↗

NASA NTRS2024

Role of Oxygen Fugacity on the Melting Properties of Enstatite Chondrites and Implications for Mercury’s Magmatic Evolution

Mercury, the innermost terrestrial planet, is the most reduced planet in our solar system. Insights from MESSENGER mission data revealed the presence of several distinct geochemical terranes, evidence of complex magmatic processes and collisional processes exposing subsurface materials. Surface chemical analysis indicated elevated S (~2-3 wt%) and low FeO (~1.5 wt%) concentrations. The high sulfur concentration indicates reduced conditions with an average of 5.4 log units below the Iron-Wüstite (IW) oxygen fugacity ( O 2 ) buffer (IW-5.4). Surface compositions also show a range in redox conditions during mantle melting and eruption, with inferred log f O 2 , ranging from IW-6.5 to IW-3.5. The effects of oxygen fugacity on magmatic differentiation are poorly constrained, despite their significance in our understanding of mantle-crust differentiation in the solar system. Enstatite High-Fe (EH) chondrites are very reduced undifferentiated meteorites with elevated concentrations of Fe and volatiles like S, Cl, Na, and K as compared to other chondrites. These characteristics suggest that EH chondrites are a potential analog for Mercury’s building blocks. However, the comparison of Mercury’s surface composition with melting products of EH chondrites is necessary to determine whether Mercury surface materials may be derived from EH chondrite- like materials. Here, we investigate the role of f O 2 on EH melting properties and its implications for Mercury’s accretion and differentiation.

Mercury↗

NASA NTRS2004

Astrobiology of Comets

We review the current state of knowledge concerning microbial extremophiles and comets and the potential significance of comets to Astrobiology. We model the thermal history of a cometary body, regarded as an assemblage of boulders, dust, ices and organics, as it approaches a perihelion distance of - IAU. The transfer of incident energy from sunlight into the interior leads to the melting of near surface ices, some under stable porous crust, providing possible habitats for a wide range of microorganisms. We provide data concerning new evidence for indigenous microfossils in CI meteorites, which may be the remains of extinct cometary cores. We discuss the dominant microbial communities of polar sea-ice, Antarctic ice sheet, and cryoconite environments as possible analogs for microbial ecosystems that may grow in sub-crustal pools or in ice/water films in comets.

Hoover, Richard B.↗

NASA NTRS2021

Composition of Organics on Asteroid (101955) Bennu

Context: The Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) mission detected an infrared absorption at 3.4μm on near-Earth asteroid(101955) Bennu. This absorption is indicative of carbon species, including organics, on the sur-face. Aims: We aim to describe the composition of the organic matter on Bennu by investigating the spectral features in detail. Methods: We use a curated set of spectra acquired by the OSIRIS-REx Visible and InfraRed Spectrometer (OVIRS) that have features near 3.4μm (3.2 to 3.6μm) attributed to organics. We assess the shapes and strengths of these absorptions in the context of laboratory spectra of extraterrestrial organics and analogs. Results: We find spectral evidence of aromatic and aliphatic CH bonds. The absorptions are broadly consistent in shape and depth with those associated with insoluble organic matter in meteorites. Given the thermal and space weathering environments on Bennu, it is likely that the organics have not been exposed for long enough to substantially decrease the H/C and destroy all aliphatic molecules.

minor planets↗

NASA NTRS2013

The Effects of Oxygen Fugacity on the Crystallization Sequence and Cr Partitioning of an Analog Y-98 Liquid

Interpreting the relationship between "enriched" olivine-phyric shergottites (e.g. NWA 1068/1110) and the "enriched" pyroxene-plagioclase shergottites (e.g. Shergotty, Los Angeles) is problematic. Symes et al. [1] and Shearer et al. [2]) proposed that the basaltic magma that crystallized to produce olivine-phyric shergottite NWA 1068/1110 could produce pyroxene-plagioclase shergottites with additional fractional crystallization. However, additional observations indicate that the relationship among the enriched shergottites may be more complex [1-3]. For example, Herd [3] concluded that some portion of the olivine megacrysts in this meteorite was xenocrystic in origin, seemingly derived from more reduced basaltic liquids. This conclusion may imply that a variety of complex processes such as magma mixing, entrainment, and assimilation may play important roles in the petrologic history of these meteorites. It is therefore possible that these processes have obscured the petrogenetic linkages between the enriched olivine-phyric shergottites and the pyroxene-plagioclase shergottites. As a first order step in attempting to unravel these petrologic complexities, this study focuses upon exploring the effect of fO2 on the crystallization history for an analog primitive shergottite liquid composition (Y98). Results from this work will provide a basis for reconstructing the record of fO2 in shergottites, its effect on both mineral chemistries and valence state partitioning, and a means for examining the role of crystallization on the petrologic linkages between olivine-phyric and pyroxene-plagioclase shergottites. A companion abstract [4] explores the behavior of V over this range of fO2.

Bell, A. S.↗

NASA NTRS2002

Side Group Addition to the PAH Coronene by UV Photolysis in Cosmic Ice Analogs

Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

Bernstein, Max P.↗

NASA NTRS2014

Formation of Nucleobases from the UV Irradiation of Pyrimidine in Astrophysical Ice Analogs

Nucleobases are the informational subunits of DNA and RNA. They consist of Nheterocycles that belong to either the pyrimidine-base group (uracil, cytosine, and thymine) or the purinebase group (adenine and guanine). Several nucleobases, mostly purine bases, have been detected in meteorites [1-3], with isotopic signatures consistent with an extraterrestrial origin [4]. Uracil is the only pyrimidine-base compound formally reported in meteorites [2], though the presence of cytosine cannot be ruled out [5,6]. However, the actual process by which the uracil was made and the reasons for the non-detection of thymine in meteorites have yet to be fully explained. Although no N-heterocycles have ever been observed in the ISM [7,8], the positions of the 6.2-μm interstellar emission features suggest a population of such molecules is likely to be present [9]. In this work we study the formation of pyrimidine-based molecules, including the three nucleobases uracil, cytosine, and thymine from the ultraviolet (UV) irradiation of pyrimidine in ices consisting of several combinations of H(sub2)O, NH(sub3), CH(sub3)OH, and CH(sub4) at low temperature, in order to simulate the astrophysical conditions under which prebiotic species may be formed in the interstellar medium, in the protosolar nebula, and on icy bodies of the Solar System.

UV Irradiation↗

NASA NTRS2010

Ultraviolet Irradiation of Pyrimidine in Interstellar Ice Analogs: Formation and Photo-Stability of Nucleobases

Astrochemistry laboratory experiments recently showed that molecules of prebiotic interest can potentially form in space, as supported by the detection of amino acids in organic residues formed by the UV photolysis of ices simulating interstellar and cometary environments (H2O, CO, CO2, CH3OH, NH3, etc.). Although the presence of amino acids in the interstellar medium (ISM) is still under debate, experiments and the detection of amino acids in meteorites both support a scenario in which prebiotic molecules could be of extraterrestrial origin, before they are delivered to planets by comets, asteroids, and interplanetary dust particles. Nucleobases, the informational subunits of DNA and RNA, have also been detected in meteorites, although they have not yet been observed in the ISM. Thus, these molecules constitute another family of prebiotic compounds that can possibly form via abiotical processes in astrophysical environments. Nucleobases are nitrogen-bearing cyclic aromatic species with various functional groups attached, which are divided into two classes: pyrimidines (uracil, cytosine, and thymine) and purines (adenine and guanine). In this work, we study how UV irradiation affects pyrimidine mixed in interstellar ice analogs (H2O, NH3, CH3OH). In particular, we show that the UV irradiation of H2O:pyrimidine mixtures leads to the production of oxidized compounds including uracil, and show that both uracil and cytosine are formed upon irradiation of H2O:NH3:pyrimidine mixtures. We also study the photostability of pyrimidine and its photoproducts formed during these experiments.

Nuevo, Michel↗

NASA NTRS2004

Analytical Protocols for Analysis of Organic Molecules in Mars Analog Materials

A range of analytical techniques and protocols that might be applied b in situ investigations of martian fines, ices, and rock samples are evaluated by analysis of organic molecules m Mars analogues. These simulants 6om terrestrial (i.e. tephra from Hawaii) or extraterrestrial (meteoritic) samples are examined by pyrolysis gas chromatograph mass spectrometry (GCMS), organic extraction followed by chemical derivatization GCMS, and laser desorption mass spectrometry (LDMS). The combination of techniques imparts analysis breadth since each technique provides a unique analysis capability for Certain classes of organic molecules.

Mahaffy, Paul R.↗

NASA NTRS1981

Effects of photometric geometry on spectral reflectance measurements

Progress is reported in obtaining valuable results needed for the full interpretation of the spectral reflectance curves of solar system objects. The degree to which photometric geometry affects spectral reflectance curves was demonstrated. Various forms of photometric functions were compared and a function adequate for describing the scattering properties of low and moderately reflecting materials was developed and applied in a study of the phase coefficients of various materials, as well as in a study of how the shape of a body affects the spectral reflectance properties. The adequacy of the photometric function for Mars-like analogs was studied. The goniometer system is being converted to a computer driven mode. As soon as computer controls are integrated in the goniometer, the phase dependence 0.95 micron feature in meteorite spectra is scheduled to begin.

Veverka, J.↗

NASA NTRS2003

Thermal Analysis of Acicular Shaped Magnetite

We are in the process of developing a database on the thermal properties of well-characterized Martian analog materials in support of future Mars surface missions. The database contains the thermal behaviors of these analog materials under reduced and Earth ambient pressures. Magnetite in planetary materials has received considerable attention in recent years since the identification of fine grain single-domain magnetite in Martian meteorite ALH84001 and their possible link to past life on Mars (i.e., possible biominerals of magnetotactic bacteria). Because of its possible importance to Mars science, we report here the thermal properties of magnetite particles with acicular morphology, i.e., needle-shaped magnetite. Acicular shaped magnetite can be commercially produced from goethite (FeOOH) as the starting material via a H2 reduction process. However, instead of using this process or procedure, we report here on the thermal characterization of acicular magnetite formed under reducing conditions from well-characterized needle-shaped goethite at low temperature in controlled CO-CO2 1-bar atmosphere gas mixing furnaces.

Lauer, H. V., Jr.↗