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NASA NTRS2010

Probing Cometary Chemistry with ALMA

Comets are considered to bear the record of the primitive Solar nebula as remnants of planetesimals that formed the outer planets. To date there are just over two dozen known cometary species compared to the >150 known interstellar molecules. This is likely due to the challenges posed when attempting to measure the composition of these small bodies. With the significant improvement in sensitivity, ALMA will likely enable the detection of new molecules to help us gain better understanding of the chemical complexity found in comets. This advancement in sensitivity will also assist in the measurement of isotope ratios in various species. These values are imperative for determining the conditions during cometary formation as well as provide insight into ongoing speculations of parent species, the possible delivery of H2O to Earth, and a direct comparison to protostellar disk chemistry. The high angular resolution obtained with ALMA will be capable of resolving any compact distributions or density enhancements in the more extended distribution that may lead to a better understanding of the formation of these species in the outer coma. By studying comet compositions we gain insight into the composition of the early Solar System as well as their astrobiological implications.

Milam, Stefanie N.↗
NASA NTRS2010

The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust

Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar abundances. The latter observation may indicate a decoupling of the silicate and sulfide components in grains that condense in stellar outflows. The amorphous silicate grains described here were not extensively affected by irradiation, sputtering, or thermal processing and may represent relatively pristine circumstellar grains. They are strong candidates for the "dirty silicates" in astronomical observations of circumstellar dust shells. The polycrystalline grains were originally amorphous silicate grains that were likely annealed in the early solar nebula but the processing was not sufficient to erase their anomalous oxygen isotopic compositions.

Keller, L. P.↗
NASA NTRS2010

Comparison of the Organic Composition of Cometary Samples with Residues Formed from the UV Irradiation of Astrophysical Ice Analogs

The NASA Stardust mission successfully collected material from Comet 81P/Wild 2 [1], including authentic cometary grains [2]. X-ray absorption near-edge structure (XANES) spectroscopy analysis of these samples indicates the presence of oxygen-rich and nitrogen-rich organic materials, which contain a broad variety of functional groups (carbonyls, C=C bonds, aliphatic chains, amines, arnides, etc.) [3]. One component of these organics appears to contain very little aromatic carbon and bears some similarity to the organic residues produced by the irradiation of ices of interstellar/cometary composition, Stardust samples were also recently shown to contain glycine, the smallest biological amino acid [4]. Organic residues produced froth the UV irradiation of astrophysical ice analogs are already known to contain a large suite of organic molecules including amino acids [5-7], amphiphilic compounds (fatty acids) [8], and other complex species. This work presents a comparison between XANES spectra measured from organic residues formed in the laboratory with similar data of cometary samples collected by the Stardust mission

Milam, S. N.↗
NASA NTRS2009

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the formation of more complex prebiotic organic compounds such as amino acids. After a 7-year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrumentation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectrometry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of prebiotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GCQMS/ IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗
NASA NTRS2010

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the forn1ation of more complex prebiotic organic compounds such as amino acids. After a 7 -year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrun1entation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectron1etry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of pre biotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GC-QMS/IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗
NASA NTRS2011

A Newly Developed Fluorescence Model for C2H6 v5 and Application to Cometary Spectra Acquired with NIRSPEC at Keck II

Accurate rotational temperatures are essential for extracting production rates for parent volatiles in comets. Two strong bands of ethane (v7 at 2985.39/cm and v5 at 2895.67/cm) are seen in infrared cometary spectra, but the Q-branches of v7 are not resolved by current instruments and cannot provide an accurate rotational temperature with current models.We developed a fluorescence model for the C2H6 v5 band that can be used to derive a rotational temperature.We applied our C2H6 5 model to high-resolution infrared spectra of the comets C/2004 Q2 Machholz and C/2000 WM1 (LINEAR), acquired with the Near-infrared Echelle Spectrograph on the Keck II telescope. We demonstrate agreement among the rotational temperatures derived from C2H6 v5 and other species, and between mixing ratios derived from C2H6 v5 and C2H6 v7. As a symmetric hydrocarbon, C2H6 is observed only in the infrared, and it is now the fifth molecule (along with H2O, HCN, CO, and H2CO) for which we can derive a reliable rotational temperature from cometary infrared spectra.

Radeva, Yana L.↗
NASA NTRS2015

Presolar Materials in a Giant Cluster IDP of Probable Cometary Origin

Chondritic porous interplanetary dust particles (CP-IDPs) have been linked to comets by their fragile structure, primitive mineralogy, dynamics, and abundant interstellar materials. But differences have emerged between 'cometary' CP-IDPs and comet 81P/Wild 2 Stardust Mission samples. Particles resembling Ca-Al-rich inclusions (CAIs), chondrules, and amoeboid olivine aggregates (AOAs) in Wild 2 samples are rare in CP-IDPs. Unlike IDPs, presolar materials are scarce in Wild 2 samples. These differences may be due to selection effects, such as destruction of fine grained (presolar) components during the 6 km/s aerogel impact collection of Wild 2 samples. Large refractory grains observed in Wild 2 samples are also unlikely to be found in most (less than 30 micrometers) IDPs. Presolar materials provide a measure of primitive-ness of meteorites and IDPs. Organic matter in IDPs and chondrites shows H and N isotopic anomalies attributed to low-T interstellar or protosolar disk chemistry, where the largest anomalies occur in the most primitive samples. Presolar silicates are abundant in meteorites with low levels of aqueous alteration (Acfer 094 approximately 200 ppm) and scarce in altered chondrites (e.g. Semarkona approximately 20 ppm). Presolar silicates in minimally altered CP-IDPs range from approximately 400 ppm to 15,000 ppm, possibly reflecting variable levels of destruction in the solar nebula or statistical variations due to small sample sizes. Here we present preliminary isotopic and mineralogical studies of a very large CP-IDP. The goals of this study are to more accurately determine the abundances of presolar components of CP-IDP material for comparison with comet Wild 2 samples and meteorites. The large mass of this IDP presents a unique opportunity to accurately determine the abundance of pre-solar grains in a likely cometary sample.

Messenger, S.↗
NASA NTRS2013

Constraining Cometary Crystal Shapes from IR Spectral Features

A major challenge in deriving the silicate mineralogy of comets is ascertaining how the anisotropic nature of forsterite crystals affects the spectral features' wavelength, relative intensity, and asymmetry. Forsterite features are identified in cometary comae near 10, 11.05-11.2, 16, 19, 23.5, 27.5 and 33 microns [1-10], so accurate models for forsterite's absorption efficiency (Qabs) are a primary requirement to compute IR spectral energy distributions (SEDs, lambdaF lambda vs. lambda) and constrain the silicate mineralogy of comets. Forsterite is an anisotropic crystal, with three crystallographic axes with distinct indices of refraction for the a-, b-, and c-axis. The shape of a forsterite crystal significantly affects its spectral features [13-16]. We need models that account for crystal shape. The IR absorption efficiencies of forsterite are computed using the discrete dipole approximation (DDA) code DDSCAT [11,12]. Starting from a fiducial crystal shape of a cube, we systematically elongate/reduce one of the crystallographic axes. Also, we elongate/reduce one axis while the lengths of the other two axes are slightly asymmetric (0.8:1.2). The most significant grain shape characteristic that affects the crystalline spectral features is the relative lengths of the crystallographic axes. The second significant grain shape characteristic is breaking the symmetry of all three axes [17]. Synthetic spectral energy distributions using seven crystal shape classes [17] are fit to the observed SED of comet C/1995 O1 (Hale-Bopp). The Hale-Bopp crystalline residual better matches equant, b-platelets, c-platelets, and b-columns spectral shape classes, while a-platelets, a-columns and c-columns worsen the spectral fits. Forsterite condensation and partial evaporation experiments demonstrate that environmental temperature and grain shape are connected [18-20]. Thus, grain shape is a potential probe for protoplanetary disk temperatures where the cometary crystalline forsterite formed. The forsterite crystal shapes (equant, b-platelets, c-platelets, b-columns - excluding a- and c-columns) derived from our modeling [17] of comet Hale- Bopp, compared to laboratory synthesis experiments [18], suggests that these crystals are high temperature condensates. By observing and modeling the crystalline features in comet ISON, we may constrain forsterite crystal shape(s) and link to their formation temperature(s) and environment(s).

anisotropic crystal↗
NASA NTRS2015

The Time-Dependent Chemistry of Cometary Debris in the Solar Corona

Recent improvements in solar observations have greatly progressed the study of sungrazing comets. They can now be imaged along the entirety of their perihelion passage through the solar atmosphere, revealing details of their composition and structure not measurable through previous observations in the less volatile region of the orbit further from the solar surface. Such comets are also unique probes of the solar atmosphere. The debris deposited by sungrazers is rapidly ionized and subsequently influenced by the ambient magnetic field. Measuring the spectral signature of the deposited material highlights the topology of the magnetic field and can reveal plasma parameters such as the electron temperature and density. Recovering these variables from the observable data requires a model of the interaction of the cometary species with the atmosphere through which they pass. The present paper offers such a model by considering the time-dependent chemistry of sublimated cometary species as they interact with the solar radiation field and coronal plasma. We expand on a previous simplified model by considering the fully time-dependent solutions of the emitting species' densities. To compare with observations, we consider a spherically symmetric expansion of the sublimated material into the corona and convert the time-dependent ion densities to radial profiles. Using emissivities from the CHIANTI database and plasma parameters derived from a magnetohydrodynamic simulation leads to a spatially dependent emission spectrum that can be directly compared with observations. We find our simulated spectra to be consistent with observation.

sun: corona↗
NASA NTRS2017

Cometary Dust: The Diversity of Primitive Matter

The connections between comet dust and primitive chondrites from asteroids has strengthened considerably over the past decade. Understanding the importance of the connections between Stardust samples and chondrites requires geochemistry lingo as well as a perspective of other cometary dust samples besides Stardust. We present the principal findings of an extensive review prepared for by us for the June 2016 "Cometary Science After Rosetta" meeting at The Royal Society, London.

asteroids↗
NASA NTRS2017

Interstellar and Solar Nebula Materials in Cometary Dust

Laboratory studies of cometary dust collected in the stratosphere and returned from comet 81P/Wild 2 by the Stardust spacecraft have revealed ancient interstellar grains and molecular cloud organic matter that record a range of astrophysical processes and the first steps of planetary formation. Presolar materials are rarer meteorites owing to high temperature processing in the solar nebula and hydrothermal alteration on their asteroidal parent bodies. The greater preservation of presolar materials in comets is attributed to their low accretion temperatures and limited planetary processing. Yet, comets also contain a large complement of high temperature materials from the inner Solar System. Owing to the limited and biased sampling of comets to date, the proportions of interstellar and Solar System materials within them remains highly uncertain. Interstellar materials are identified by coordinated isotopic, mineralogical, and chemical measurements at the scale of individual grains. Chondritic porous interplanetary dust particles (CP IDPs) that likely derive from comets are made up of 0.1 - 10 micron-sized silicates, Fe-Ni-sulfides, oxides, and other phases bound by organic material. As much as 1% of the silicates are interstellar grains that have exotic isotopic compositions imparted by nucleosynthetic processes in their parent stars. Crystalline silicates in CP IDPs dominantly have normal isotopic compositions and probably formed in the Solar System. 81P samples include isotopically normal refractory minerals that resemble Ca-Al rich inclusions and chondrules common in meteorites. The origins of sub-micron amorphous silicates in IDPs are not certain, but at least a few % of them are interstellar grains. The remainder have isotopic compositions consistent with Solar System origins and elemental compositions that are inconsistent with interstellar grain properties, thus favoring formation in the solar nebula [4]. The organic component in comets and primitive meteorites has large enrichments in D/H and N-15/N-14 relative to terrestrial materials. These isotopic signatures are probably due to low temperature chemical processes in cold molecular clouds or the outermost reaches of the protoplanetary disk. The greatest isotopic anomalies are found in sub-micron organic nanoglobules that show chemical signatures of interstellar chemistry. The observation that cometary dust is mostly composed of isotopically normal minerals within isotopically anomalous organic matter is difficult to reconcile with the formation models of each component. The mineral component likely formed in high temperature processes in the inner Solar System, while the organic fraction shows isotopic and chemical signatures of formation near 10 K. Studying more primitive remnants of the Solar System starting materials would help in resolving this paradox. Comets formed across a vast expanse of the outer disk under differing thermal and collisional regimes, and some are likely to be better preserved than others. Finding truly pristine aggregates of presolar materials may require return of a pristine sample of comet nucleus material.

Messenger, Scott↗
NASA NTRS2018

The Diversity of Carbon in Cometary Refractory Dust Particles

When comparing the dark icy surfaces of outer solar system small bodies and the composition of carbonaceous chondrites derived from dark asteroids we find a significant discrepancy in the assessed amounts of elemental carbon: up to 80% amorphous carbon is used to model the dark surfaces of Kuiper Belt Objects and Centaurs whereas at most 5% of elemental carbon is found in carbonaceous chondrites. If we presume that regimes of comet nuclei formation are analogous to disk regimes where other outer solar system ice-rich bodies formed then we can turn to comet dust to gain insights into the diversity in the concentration and forms of carbon available in the outer disk. Comet dust offers important insights into the diversity in the amounts and forms of carbon that were incorporated into aggregate dust particles in the colder parts of the protoplanetary disk out of which comet nuclei accreted. Comet nuclei are amongst the most primitive bodies because they have remained cold and unequilibrated. Comet dust particles reveal the presence of forms of elemental carbon and of soluble and insoluble organic matter, and in a great diversity of concentrations from very little, e.g., Stardust samples of comet 81P/Wild 2, to 80% by volume for Ultra Carbonaceous Antarctic Micro Meteorites (UCAMMs). Cometary outbursts and/or jet activity also demonstrate variations in the concentration of carbon in the grains at different grain sizes within a single comet. We review the diversity of carbon-bearing dust grains in cometary samples, flyby measurements and deduced from remote-sensing to enrich the discussion about the diversity of carbonaceous matter available in the outer ice-rich disk at the time of comet nuclei formation.

Wooden, D. H.↗
NASA NTRS2020

Volatile Composition and Outgassing in C/2018 Y1 (IWAMOTO): Extending Detection Limits for High-Resolution IR Cometary Spectroscopy at the NASA-IRTF

We used iSHELL, the powerful high-resolution ( λ/Δλ~ 40,000) cross-dispersed IR spectrograph at the NASA-IRTF to measure the native ice composition and outgassing of moderately bright, long-period comet C/2018 Y1 (Iwamoto) (hereafter Y1) within weeks of its discovery. We measured production rates for H2O, and production rates and abundance ratios relative to H2O for eight trace molecules, including the most complete measure of cometary CH4 achieved to date. Compared with mean abundances measured among comets, our study revealed enriched CH3OH and C2H6 yet depleted CO and C2H2, perhaps indicating highly efficient H- atom addition on interstellar grains prior to their incorporation into the nucleus. The combined high spectral resolving power and broad spectral coverage of iSHELL allowed characterizing cometary composition using only three instrument settings, and its long-slit coverage allowed comparing the spatial distributions of molecular emissions and dust continuum.

DiSanti, M. A.↗
NASA NTRS1995

Dynamics of Cometary Dust

The paper reviews recent progress in understanding of the diversity of cometary dust features (such as jets, fans, halos, and envelopes), which are products of particle ejections from discrete emission regions on the nucleus surface.

comets cometary dust↗
NASA NTRS2016

Cometary Origin of Atmospheric Methane Variations on Mars Unlikely

The detection of methane in the atmosphere of Mars was first reported in 2004. Since then a number of independent observations of methane have been reported, all showing temporal variability. Up until recently, the origin of methane was attributed to sources either indigenous to Mars or exogenous, where methane is a UV degradation byproduct of organics falling on to the surface. Most recently, a new hypothesis has been proposed that argues that the appearance and variation of methane are correlated with specific meteor events at Mars. Indeed, extraplanetary material can be brought to a planet when it passes through a meteoroid stream left behind by cometary bodies orbiting the Sun. This occurs repeatedly at specific times in a planet's year as streams tend to be fairly stable in space. In this paper, we revisit this latest hypothesis by carrying out a complete analysis of all available data on Mars atmospheric methane, including the very recent data not previously published, together with all published predicted meteor events for Mars. Whether we consider the collection of individual data points and predicted meteor events, whether we apply statistical analysis, or whether we consider different time spans between high methane measurements and the occurrence of meteor events, we find no compelling evidence for any correlation between atmospheric methane and predicted meteor events.

methane↗