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NASA NTRS2007

Organics Captured from Comet Wild 2 by the Stardust Spacecraft

Organics found in Comet Wild 2 samples show a heterogeneous and unequilibrated distribution in abundance and composition. Some are similar, but not identical, to those in interplanetary dust particles (IDPs) and carbonaceous meteorites. A new class of aromatic-poor organic material is also present. The organics are rich in O and N compared to meteoritic organics. Aromatic compounds are present, but the samples tend to be relatively poorer in aromatics than meteorites and IDPs. D and 15N suggest that some organics have an interstellar/protostellar heritage. While the variable extent of modification of these materials by impact capture is not yet fully constrained, a remarkably diverse suite of organic compounds is present and identifiable within the returned samples.

Sandford, Scott A.↗
NASA NTRS2007

Ratios of Biogenic Elements for Distinguishing Recent from Fossil Microorganisms

The ability to distinguish possible microfossils from recent biological contaminants is of great importance to Astrobiology. In this paper we discuss the application of the ratios of life critical biogenic elements (C/O; C/N; and C/S) as determined by Energy Dispersive X-ray Spectroscopy (EDS) to this problem. Biogenic element ratios will be provided for a wide variety of living cyanobacteria and other microbial extremophiles, preserved herbarium materials, and ancient biota from the Antarctic Ice Cores and Siberian and Alaskan Permafrost for comparison with megafossils and microfossils in ancient terrestrial rocks and carbonaceous meteorites.

Hoover, Richard B.↗
NASA NTRS2008

Are Fullerenes Relevant to Cosmochemistry? A New Finding

The abundances of noble gases found in primitive, carbonaceous meteorites are unexpected when compared with our Sun. Known as Q-gases (Q for some unknown carrier dubbed quintessence ), this anomaly has remained a mystery since it was discovered in 1975. Q-gases are characterized by increasing depletions with decreasing atomic number (Z) relative to solar noble gases and normalized to 132Xe (Figure 1). This Q-gas mass fractionation is unexplained, and its investigation is important to understanding the origin of the solar system. However, the subject is fraught with controversy, in part due to the complex nature of Q and in part due to claims of some researchers that cannot be reproduced by other investigators. The topic is discussed in numerous places [e.g., 1-4], with models of Q falling into two basic categories, both involving carbon entrapment of noble gases. First (Group A), there is the conservative two-dimensional view that Q-gases are adsorbed or sorbed onto a "labyrinth" of graphite or carbon grains [5-9], or they undergo active capture onto growing surfaces [6]. Second (Group B), there is the view holding to the remarkable property of carbon discovered in 1985. Carbon can curl up into closed geometries of hexagon- and pentagon-shaped carbon-ring configurations, a property ignored completely by Group A. Group B thinks of Q as a three-dimensional structure of endohedral carbon cages like fullerenes, carbon onions, or some class of carbon nanotubes [3, 4, 10]. Group B does not exclude Group A effects.

Wilson, T. L.↗
NASA NTRS2008

Miniature Mass Spectrometers on Space and Planetary Missions

Space flight mass spectrometers contribute our understanding of the origin and evolution of our solar system and even of life itself. This fundamental role has motivated increasing interest in miniature mass spectrometry for planetary missions. Several remarkable new instruments are en route or under development to investigate the composition of planetary bodies such as Mars and comets. For instance, the Sample Analysis at Mars (SAM) suite on the 2009 Mars Science Laboratory (MSL) mission includes a quadrupole mass spectrometer with a sophisticated gas processing system as well as pyrolysis and chemical derivatization protocols for solid samples. Future missions will require even lighter, lower power, and yet more capable mass spectrometers, particularly to analyze samples in situ on planetary surfaces. We have been developing laser-based mass spectrometers for elemental and organic/molecular analysis of rock, ice, or fine particle samples. These typically use time-of-flight (TOF) mass analyzers, which are readily miniaturized and can detect both atomic species and complex organics that occur in a variety of planetary materials. For example, nonvolatile polycyclic aromatic hydrocarbons and kerogen-like macromolecular carbon are found in some carbonaceous meteorites, which derived from asteroid parent bodies. A single focused laser pulse is able to volatilize and ionize some of these compounds for direct TOF analysis. While this is possible without any sample preparation or contact, sensitivity and quantitative performance can improve significantly with some sample handling. As such we have also been examining robotic mechanisms and protocols to accompany space flight mass spectrometers. In addition, sensors in early development may significantly improve these capabilities, via use of techniques such as switchable polarity, ambient pressure, or resonant ionization; tandem mass spectrometry (TOF or ion trap); and chemical imaging.

Brinckerhoff, William↗
NASA NTRS2009

Panel Discussion: Life in the Cosmos

Water appears to be essential to all life on Earth. For this reason, "Follow the Water" has been adopted as a mantra for the search for Life in the Cosmos. Expeditions have helped to establish the limits and biodiversity of life in the most extreme environments on Earth. Microbial extremophiles inhabit acidic streams; hypersaline and hyperalkaline lakes and pools; the cold deep sea floor, permafrost, rocks, glaciers, and perennially ice-covered lakes of the polar environments; geysers, volcanic fumaroles, hydrothermal vents and hot rocks deep within the Earth's crust. The ESA Venus Express Spacecraft entered Venusian Orbit in 2006 and continues to produce exciting results. The Visible and Infrared Thermal Imaging Spectrometer (VIRTIS) instrument made the first detection of hydroxyl in the atmosphere of Venus, indicating it is much more similar to Earth and Mars than previously thought. Huge hurricane-like vortices have been found above the poles of the planet and as yet unidentified UV absorbers that form mysterious dark bands in the upper atmosphere. At 70 km and below, water vapor and sulfur dioxide combine to form sulfuric acid droplets that create a haze above the cloud tops. Thermophilic acidophiles, such as have recently been discovered on Earth, could possibly survive in the hot sulfuric acid droplets that exist in the upper atmosphere of Venus. In order to understand how to search for life elsewhere in the Solar System, over 40 VIRTIS images of Earth from Venus have been obtained to search for evidence of life on Earth. The signatures of water and molecular Oxygen were detected in the Earth s atmosphere, but the atmosphere of Venus also exhibits these signatures. The water and water ice are far more abundant on comet, the polar caps and permafrost of Mars and the icy moons of Jupiter and Saturn. These "frozen worlds" of our Solar System, are much more promising regimes where extant or extinct microbial life may exist. The ESA Mars Advanced Radar for Subsurface and Ionospheric Sounding (MARSIS) probe has found that both the North and South Polar Caps of Mars are approximately 3.5 km thick and are composed almost entirely of water ice. In winter, a thin dry ice layer covers the caps, but it sublimates directly to CO2 in the spring. The ESA Mars Express Orbiter images reveal Rupes Tenuis to be a vast snow-laden region on the southern edge of the Martian North Polar Cap. The Mars Exploration Rover Spirit found alkaline volcanic rocks in the Gusev Crater and the Phoenix Mars Lander has shown that the soil of Mars is much more alkaline than previously expected. The Phoenix Mars Lander has also made direct observations of frozen and liquid water on Mars. It is known that microorganisms from Alaska, Siberia and Antarctica can remain alive frozen in permafrost or ice for long periods of time. These discoveries increase the possibility that the Labeled Release Experiment may have discovered life on Mars during the Viking Mission and provide strong impetus for the return of life detection experiments to Mars. Changes in the spin rate of Saturn's moon Titan indicate that it may also harbor a 300 km thick liquid water ocean beneath its icy crust. The NASA/ESA/Italian Space Agency Cassini Spacecraft has imaged geysers containing water vapor, methane, carbon dioxide and organics erupting from the "tiger stripe" regions near the South Pole of Saturn's moon Enceladus. The high temperatures observed, the water vapor and large number of ice particles expelled suggest that a liquid water lake may exist beneath the "tiger stripe" ice cracks of Enceladus. The NASA Deep Impact probe found the surface temperature of comet 9P/Temple 1 at 1.5 AY was slightly above the ice/water phase change temperature (273 K). This suggests melting of water ice near the comet surface. A spectrometer the spacecraft detected a mixture of clay and carbonate minerals (that form in the presence of liquid water) streaming off the comet after the collision with the pactor. The study of chemical and mineral biomarkers, chiral amino acids and possible indigenous microfossils in SNC and carbonaceous meteorites continues. These results suggest that comets should be considered prime targets in the search for Life in the Cosmos. The ESA Rosetta mission is on track to rendezvous with comet 67P/Churyumov-Gerasimenko. The recent space observations combined with new information about the ability of microbial extremophiles to thrive in polar environments suggest that life may be far more widely distributed in the Cosmos than previously thought possible. The Panelists will review recent discoveries and provide their own insights about Life in the Cosmos -- followed by a question and answer session with the audience.

Hoover, Richard B.↗
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 NTRS2011

The Importance of Sample Return in Establishing Chemical Evidence for Life on Mars or Other Solar System Bodies

The search for evidence of life on Mars and elsewhere will continue to be one of the primary goals of NASA s robotic exploration program over the next decade. NASA and ESA are currently planning a series of robotic missions to Mars with the goal of understanding its climate, resources, and potential for harboring past or present life. One key goal will be the search for chemical biomarkers including complex organic compounds important in life on Earth. These include amino acids, the monomer building blocks of proteins and enzymes, nucleobases and sugars which form the backbone of DNA and RNA, and lipids, the structural components of cell membranes. Many of these organic compounds can also be formed abiotically as demonstrated by their prevalence in carbonaceous meteorites [1], though, their molecular characteristics may distinguish a biological source [2]. It is possible that in situ instruments may reveal such characteristics, however, return of the right sample (i.e. one with biosignatures or having a high probability of biosignatures) to Earth would allow for more intensive laboratory studies using a broad array of powerful instrumentation for bulk characterization, molecular detection, isotopic and enantiomeric compositions, and spatially resolved chemistry that may be required for confirmation of extant or extinct Martian life. Here we will discuss the current analytical capabilities and strategies for the detection of organics on the Mars Science Laboratory (MSL) using the Sample Analysis at Mars (SAM) instrument suite and how sample return missions from Mars and other targets of astrobiological interest will help advance our understanding of chemical biosignatures in the solar system.

Glavin, D. P.↗
NASA NTRS2011

Primordial Synthesis of Amines and Amino Acids in a 1958 Miller H2S-Rich Spark Discharge Experiment

Archived samples from a previously unreported 1958 Stanley Miller electric discharge experiment containing hydrogen sulfide (H2S) were recently discovered and analyzed using high-performance liquid chromatography and time-of-flight mass spectrometry. We report here the detection and quantification of primary amine-containing compounds in the original sample residues, which were produced via spark discharge using a gaseous mixture of H2S, CH4, NH3, and CO2. A total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordia! environments. The relative yield of some amino acids, in particular the isomers of aminobutyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments.

Parker, Eric T.↗
NASA NTRS2011

Life in the Cosmos

Discoveries by NASA & ESA Spacecraft provide additional evidence for present day liquid water on Mars and water/ice jets on Comets & Enceladus. Stardust mineralogical data support the Hypothesis that water-rich Comets represent parent bodies for the CI1 Carbonaceous Meteorites. Undetectable Nitrogen & low O/C ratios in Filaments found in CI1 Orgueil meteorite rule out Modern Biological Contamination Hypothesis.

Hoover, Richard B.↗
NASA NTRS2011

New Insights into Prebiotic Chemistry from Old Archived Miller Extracts

Following the discovery of an archived set of samples from Stanley Miller's early experiments, analyses were undertaken to better understand the diversity of compounds produced from electric discharges acting on reducing gas mixtures. The paper chromatography methods that Miller used in the 1950s were only capable of detecting a few amino acids and were unable to provide substantial quantitative data relative to today's techniques. Current analytical techniques are much more sensitive and selective, and are capable of precisely quantifying a much larger range of amino acids and their enantiomeric abundances. In one study, preserved dried samples produced by Miller using a lesser-known volcanic apparatus which differed from Miller's classic apparatus in that it utilized an aspirator that injected steam into the electric discharge chamber, simulating a volcanic eruption. The volcanic apparatus produced a wider variety of amino acids than the classic configuration. Prebiotic compounds synthesized in these environments may have locally accumulated where they could have undergone further processing. An additional preserved set of samples from an experiment conducted in 1958 were also found in Miller's archived collection. These samples which had been generated using a mixture of CH4, NH3, H2S and CO2 were collected, catalogued, and stored by Miller, but for unknown reasons were never studied. In our analyses a total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordial environments. The relative yield of some amino acids, in particular the isomers of amino butyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller in these experiments may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments. Although experiments using a variety of gases as components of the primordial Earth's atmospheric composition and a spark discharge apparatus configured according to Miller's original or volcanic design can be readily carried out, the unique opportunity to investigate samples prepared by the pioneer in abiotic synthesis using state of the art analytical methods is of considerable historic interest.

Parker, Eric T.↗
NASA NTRS2012

Detecting Organic Compounds Released from Iron Oxidizing Bacteria using Sample Analysis at Mars (SAM) Like Instrument Protocols

Mars is a planet of great interest for Astrobiology since its past environmental conditions are thought to have been favourable for the emergence life. At present, the Red Planet is extremely cold and dry and the surface is exposed to intense UV and ionizing radiation, conditions generally considered to be incompatible with life as we know it on Earth. It was proposed that the shallow subsurface of Mars, where temperatures can be above freezing and liquid water can exist on rock surfaces, could harbor chemolithoautotrophic bacteria such as the iron oxidizing microorganism Pseudomonas sp. HerB. The Mars Science Laboratory (MSL) mission will provide the next opportunity to carry out in situ measurements for organic compounds of possible biological origin on Mars. One instrument onboard MSL, called the Sample Analysis at Mars (SAM) instrument suite, will carry out a broad and sensitive search for organic compounds in surface samples using either high temperature pyrolysis or chemical extraction followed by gas chromatography mass spectrometry. We present gas chromatograph mass spectrometer (GC/MS) data on crushed olivine rock powders that have been inoculated with Pseudomonas sp. HerB at different concentrations ranging from approx 10(exp 2) to 10(exp 7) cells per gram. The inoculated olivine samples were heated under helium carrier gas flow at 500 C and the pyrolysis products concentrated using a SAM-like hydrocarbon trap set at -20 C followed by trap heating and analysis by GC/Ms. In addition, the samples were also extracted using a low temperature "one-pot" chemical extraction technique using N-methyl, N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) as the silylating agent prior to GC/MS analysis. We identified several aldehydes, thiols, and alkene nitriles after pyrolysis GC/MS analysis of the bacteria that were not found in the olivine control samples that had not been inoculated with bacteria. The distribution of pyrolysis products extracted from the bacteria was clearly distinct from similar GC/MS analyses of the carbonaceous meteorite Murchison that was dominated by sulfur containing aromatic compounds. A similar comparison, if organic compounds are detected by SAM on Mars, could be useful to help discriminate between meteoritic or biological origins.

Glavin, D. P.↗
NASA NTRS2014

Interstellar Organics, the Solar Nebula, and Saturn's Satellite Phoebe

The diffuse interstellar medium inventory of organic material (Pendleton et al. 1994, Pe 2002) was likely incorporated into the molecular cloud in which the solar nebula condensed. This provided the feedstock for the fo planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Saturn's satellites Phoeb open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS) on the Cass Phoebe (mean diameter 213 km) is a former TNO now orbiting Saturn. VIMS spectral maps of Phoebe's surface reveal a complex consisting of prominent aromatic (CH) and aliphatic hydrocarbon (CH2, CH3) absorption bands (3.2-3.6 μm). Phoebe is the source encircling Saturn, and from which particles (~5-20 μm size) spiral inward toward Saturn. They encounter Iapetus and Hyperion wh blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aroma abundant as aliphatic CH2+CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, com carbonaceous meteorites (Cruikshank et al. 2013). A similar excess of aromatics over aliphatics is seen in the qualitative analysis o itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 ~4, which is larger than the value found in the di as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inv understanding the content and degree of processing of that nebular material. There are other Phoebe-like TNOs that are presently b in the organic spectral region, but JWST will open that possibility for a number of objects. We now need to explore and understand organic-bearing Solar System material to the solar nebula and the inventory of ISM materials incorporated therein.

Interstellar↗
NASA NTRS2014

Interstellar Organics, the Solar Nebula, and Saturn's Satellite Phoebe

The diffuse interstellar medium inventory of organic material (Pendleton et al. 1994, Pendleton & Allamandola 2002) was likely incorporated into the molecular cloud in which the solar nebula condensed. This provided the feedstock for the formation of the Sun, major planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Saturn's satellites Phoebe, Iapetus, and Hyperion open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS) on the Cassini spacecraft at Saturn. Phoebe (mean diameter 213 km) is a former TNO now orbiting Saurn. VIMS spaectral maps of PHoebe's surface reveal a complex organic spectral signature consisting of prominent aromatic (CH) and alophatic hydrocarbon (CH2, CH3) absorption bands (3.2-3.6 micrometers). Phoebe is the source of a huge debris ring encircling Saturn, and from which particles (approximately 5-20 micrometer size) spiral inward toward Saturn. They encounter Iapetus and Hperion where they mix with and blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aromatic CH is approximately 10 times as abundant as aliphatic CH2+CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, comet particles, ad in carbonaceous meteorites (Cruikshank et al. 2013). A similar excess of aromatics over aliphatics is seen in the qualitative analysis of Hyperion and Phoebe itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 approximately 4, which is larger than the value found in the diffuse ISM (approximately 2-2.5). In so far as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inventory, it can be key to understanding the content and degree of procesing of the nebular material. There are other Phoebe-like TNOs that are presently beyond our ability to study in the organic spectral region, but JWST will open that possibility for a number of objects. We now need to explore and understand the connection of this organic-bearing Solar System material to the solar nebula the the inventory of ISM materials incorporated therein.

Interstellar↗
NASA NTRS2013

Strain Measurements of Chondrules and Refraction Inclusion in Allende

This study uses traditional strain measurement techniques, combined with X-ray computerized tomography (CT), to evaluate petrographic evidence in the Allende CV3 chondrite for preferred orientation and to measure strain in three dimensions. The existence of petrofabrics and lineations was first observed in carbonaceous meteorites in the 1960's. Yet, fifty years later only a few studies have reported that meteorites record such features. Impacts are often cited as the mechanism for this feature, although plastic deformation from overburden and nebular imbrication have also been proposed. Previous work conducted on the Leoville CV3 and the Parnallee LL3 chondrites, exhibited a minimum uniaxial shortening of 33% and 21%, respectively. Petrofabrics in Allende CV3 have been looked at before; previous workers using Electron Back Scatter Diffraction (EBSD) found a major-axis alignment of olivine inside dark inclusions and an "augen"-like preferred orientation of olivine grains around more competent chondrules

Tait, Alastair W.↗
NASA NTRS2015

PAHs in the Ices of Saturn's Satellites: Connections to the Solar Nebula and the Interstellar Medium

Aliphatic hydrocarbons and PAHs have been observed in the interstellar medium (e.g., Allamandola et al. 1985, Pendleton et al. 1994, Pendleton & Allamandola 2002, Tielens 2013, Kwok 2008, Chiar & Pendleton 2008) The inventory of organic material in the ISM was likely incorporated into the molecular cloud in which the solar nebula condensed, contributing to the feedstock for the formation of the Sun, major planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Additional organic synthesis occurred in the solar nebula (Ciesla & Sandford 2012). Saturn's satellites Phoebe, Iapetus, and Hyperion open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS) on the Cassini spacecraft at Saturn. Phoebe (mean diameter 213 km) is a former TNO now orbiting Saturn (Johnson & Lunine 2005). VIMS spectral maps of Phoebe's surface reveal a complex organic spectral signature consisting of prominent aromatic (CH) and aliphatic hydrocarbon (=CH2, -CH3) absorption bands (3.2-3.6 micrometers). Phoebe is the source of a huge debris ring encircling Saturn, and from which particles ((is) approximately 5-20 micrometers size) spiral inward toward Saturn (Verbiscer et al. 2009). They encounter Iapetus and Hyperion where they mix with and blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aromatic CH is approximately 10 times as abundant as aliphatic CH2+CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, comet particles, and in carbonaceous meteorites (Cruikshank et al. 2014). A similar excess of aromatics over aliphatics is seen in the qualitative analysis of Hyperion and Phoebe itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 (is) approximately 4, which is larger than the value found in the diffuse ISM ((is) approximately 2-2.5). Insofar as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inventory, it can be key in understanding the content and degree of processing of that nebular material. A dynamical subset of TNOs define the Kuiper Belt, from which the short-period comets originate. Particles collected from comet 81P/Wild contain PAHs with an interstellar signature of deuterium. By inference, the PAHs contained in Phoebe and now dusted on the surfaces of two other Saturn satellites share that interstellar origin. There are other Phoebe-like TNOs that are presently beyond our ability to study in the organic spectral region, but JWST will open that possibility for a number of objects.

Solar nebula↗
NASA NTRS2018

Detailed Study of the Formation of Sugar Derivatives Produced from the UV Irradiation of Astrophysical Ice Analogs

Carbonaceous meteorites such as Murchison contain a large variety of organic compounds of astrobiological interest such as amino acids, other amphiphilic compounds, functionalized nitrogen heterocycles (including nucleobases), functionalized polycylic aromatic hydro-carbons (including quinones), and sugar derivatives. The presence of such a broad variety of organics in meteorites strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is strongly supported by laboratory studies in which astrophysical ice analogs (i.e., mixtures of H2O, CO, CO2, CH3OH, CH4, NH3, etc.) are subjected to ultraviolet (UV) irradiation at low temperature (less than 15 K) to simulate cold interstellar environments. These studies have shown that the organic residues recovered at room temperature after irradiation contain organic compounds that are very similar to those found in meteorites. No systematic search for the presence of sugar derivatives in laboratory residues had been carried out until the recent detection of ribose, the sugar of RNA, as well as other sugars, sugar alcohols, and sugar acids in one residue produced from the UV irradiation of an ice mixture containing H2O, CH3OH, and NH3 at 80 K. In this work, we present a detailed study of the formation of sugar derivatives contained in organic residues that are produced from the UV irradiation of ice mixtures of different starting compositions (H2O, CH3OH, CO, CO2, and/or NH3) at less than 15 K. While the presence of sugar alcohols, sugars, and sugar acids-in some cases with up to 6 carbon atoms-could be confirmed in all these residues, their distribution was shown to vary with the composition of the starting ices. In particular, only a few ices result in the formation of sugar derivatives displaying a distribution that resembles that of meteorites, in which sugar alcohols and sugar acids are very abundant while sugars are mostly absent.

Photochemistry↗
NASA NTRS2017

Sugar Derivatives in Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

A large variety of organic compounds of astrobiological and prebiotic interest have been detected in carbonaceous meteorites. These include amino acids, carboxylic acids, amphiphiles, functionalized nitrogen heterocycles such as nucleobases, functionalized polycylic aromatic hydrocarbons such as quinones, and sugar derivatives. The sugar derivatives identified in the Murchison and Murray meteorites are mainly sugar alcohols and sugar acids, and only the smallest sugar (dihydroxyacetone) has been detected. The presence of such a variety of organics in meteorites strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is further supported by laboratory studies in which astrophysical ice analogs (mixtures of H2O, CO, CO2, CH3OH, CH4, NH3, etc.) are subjected to ultraviolet (UV) irradiation at low temperature (<15 K) to simulate cold interstellar environments. These studies show that the organic residues recovered at room temperature after irradiation contain amino acids, amphiphiles, nucleobases, sugar derivatives, as well as other complex organic compounds. The finding of such compounds under plausible interstellar conditions is consistent with the presence of organic compounds in meteorites. Until very recently, no systematic search for the presence of sugar derivatives in laboratory residues had been carried out. The detection of ribose, the sugar constituent of RNA in all living systems, as well as other sugars, sugar alcohols, and sugar acids have been recently reported in one organic residue produced from the UV irradiation of an H2O:CH3OH:NH3 (10:3.5:1) ice mixture at 80 K. In this work, we present a detailed study of organic residues produced from the UV irradiation ice mixtures of several starting compositions (containing H2O, CH3OH, CO, CO2, and/or NH3) at <15 K for their sugar derivative content. Our results confirm the presence of all 3C‒5C sugar alcohols, several 3C‒5C sugars, and all 3C‒4C sugar acids (in decreasing order of abundances) in the residues. The higher abundances of sugar alcohols in these residues suggest a pathway in which sugar alcohols are formed first, while the formation of sugars and sugar acids require more steps. Finally, our results are compared with the detection of sugars derivatives in primitive meteorites.

Astrophysical Ice Analogs↗
NASA NTRS2014

Interstellar Organics, the Solar Nebula, and Saturn's Satellite Phoebe

The diffuse interstellar medium inventory of organic material (Pendleton et al. 1994, Pendleton Allamandola 2002) was likely incorporated into the molecular cloud in which the solar nebula condensed. This provided the feedstock for the formation of the Sun, major planets, and the smaller icy bodies in the region outside Neptune's orbit (transneptunian objects, or TNOs). Saturn's satellites Phoebe, Iapetus, and Hyperion open a window to the composition of one class of TNO as revealed by the near-infrared mapping spectrometer (VIMS - Visible and Infrared Mapping Spectrometer) on the Cassini spacecraft at Saturn. Phoebe (mean diameter 213 kilometers) is a former TNO now orbiting Saturn. VIMS spectral maps of Phoebe's surface reveal a complex organic spectral signature consisting of prominent aromatic (CH) and aliphatic hydrocarbon (CH2, CH3) absorption bands (3.2-3.6 meters). Phoebe is the source of a huge debris ring encircling Saturn, and from which particles (5-20 meter size) spiral inward toward Saturn. They encounter Iapetus and Hyperion where they mix with and blanket the native H2O ice of those two bodies. Quantitative analysis of the hydrocarbon bands on Iapetus demonstrates that aromatic CH is 10 times as abundant as aliphatic CH2 plus CH3, significantly exceeding the strength of the aromatic signature in interplanetary dust particles, comet particles, and in carbonaceous meteorites (Cruikshank et al. 2013). A similar excess of aromatics over aliphatics is seen in the qualitative analysis of Hyperion and Phoebe itself (Dalle Ore et al. 2012). The Iapetus aliphatic hydrocarbons show CH2/CH3 4, which is larger than the value found in the diffuse ISM (InterStellar Matter - (2-2.5). Insofar as Phoebe is a primitive body that formed in the outer regions of the solar nebula and has preserved some of the original nebula inventory, it can be key to understanding the content and degree of processing of that nebular material. There are other Phoebe-like TNOs that are presently beyond our ability to study in the organic spectral region, but JWST (James Webb Space Telescope) will open that possibility for a number of objects. We now need to explore and understand the connection of this organic-bearing Solar System material to the solar nebula and the inventory of ISM (Interstellar Medium) materials incorporated therein.

Phoebe↗