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Amino Acids from a Comet

NASA's Stardust spacecraft returned samples from comet 81P/Wild 2 to Earth in January 2006. Examinations of the organic compounds in cometary samples can reveal information about the prebiotic organic inventory present on the early Earth and within the early Solar System, which may have contributed to the origin of life. Preliminary studies of Stardust material revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds (cometary- vs. terrestrial contamination) could not be identified. We have recently measured the carbon isotopic ratios of these amino acids to determine their origin, leading to the first detection of a coetary amino acid.

Cook, Jamie Elisla↗

Search for Organic Nanoglobules in Carbonaceous Chondrites Using Microtomography

Primitive solar materials have various organic matters. In recent years, novel organic materials called organic nanoglobules of a few hundred micrometers in typical size were discovered in carbonaceous chondrites, IDPs, and comet 81P/Wild 2. The organic globules are spherical shape and in many cases with hollow structures. Composition of the globules are mainly aromatic carbon. The isotopic anomalies of SD and 6N 15 observed in the globules indicate that they were formed from photochemical reaction to ice particles at very low temperature environment, such as molecular clouds or outer protosolar disk. Aqueous alteration of organic matters and the gamma-ray irradiation to PAH are also suggested as alternative possible formation processes. If the globules are made from organic ice particles, the hollow regions of the globules are suggested to be once filled with volatile H20-rich organic ices, while if they were formed by aqueous alteration, the hollow regions should be filled with a fluid which caused the aqueous alteration. However, fluids in the globules have not been detected so far in the previous studies. If fluids were originally preserved in the hollows, they might be lost during destructive processes of sample separation or preparation for TEM observation. X-ray computed tomography (CT) is a nondestructive method which can determine 3-D internal structures of objects. SR (synchrotron radiation)-based imaging microtomography can give submicron spatial resolution [8] and was applied to micro textures in extraterrestrial materials, such as cometary grains captured by the Stardust mission [9]. If organic globules are observed non-destructively in carbonaceous chondrites by tomography, we can check the presence of fluids in the hollows. If fluids are preserved, we may analyze chemical and isotopic compositions of the fluids. The purpose of this study is to observe organic nanoglobules using imaging tomography for future analysis.

Matsumoto, T.↗

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.↗

Correlated Microanalysis of Cometary Organic Grains Returned by Stardust

Preliminary examination (PE) of samples returned from Comet 81P/Wild 2 by the NASA Stardust mission revealed a wide variety of carbonaceous samples [e.g. 1]. Carbonaceous matter is present as inclusions, rinds, and films in polyminerallic terminal particles [2-4], as carbon-rich particles along track walls [2, 5, 6], and as organic matter in aerogel around tracks [7, 8]. The organic chemistry of these samples ranges from purely aliphatic hydrocarbons to highly-aromatic material, often modified by various organic functional groups [2, 4, 5, 9-11]. Difficulty arises when interpreting the genesis of these carbonaceous samples, since contaminants could be introduced from the spacecraft [12], aerogel [1, 8], or during sample preparation. In addition, hypervelocity capture into aerogel may have heated cometary material in excess of 1000 C, which could have significantly altered the structure and chemistry of carbonaceous matter. Fortunately, much of this contamination or alteration can be identified through correlated microanalysis with transmission electron microscopy (TEM), scanning-transmission X-ray microscopy (STXM), and nanoscale secondary ion mass spectroscopy (SIMS).

DeGregorio, B. T.↗

Stardust Interstellar Foils I1061N,1 and I1031N, 1: First Results from Automated Crater Searches and Future Analytical Possibilities

In addition to samples from comet 81P/Wild 2, NASA's Stardust mission may have returned the first samples of contemporary interstellar dust. The interstellar tray collected particles for 229 days during two exposures prior to the spacecraft encounter with Wild 2 and tracked the interstellar dust stream for all but 34 days of that time. In addition to aerogel capture cells, the tray contains Al foils that make up approx.15% of the total exposed collection surface . Interstellar dust fluxes are poorly constrained, but suggest that on the order of 12-15 particles may have impacted the total exposed foil area of 15,300 sq mm; 2/3 of these are estimated to be less than approx.1 micrometer in size . Examination of the interstellar foils to locate the small rare craters expected from these impacts is proceeding under the auspices of the Stardust Interstellar Preliminary Examination (ISPE) plan. Below we outline the automated high-resolution imaging protocol we have established for this work and report results obtained from two interstellar foils.

Zolensky, M. E.↗

Mineralogy of Stardust Track 112 Particle: Relation to Amoeboid Olivine Aggregates

The successful analysis of comet 81P/Wild 2 particles returned by the Stardust mission has revealed that the Wild 2 dust contains abundant silicate grains that are much larger than interstellar grains and appear to have formed in the inner regions of the solar nebula [1]. Wild 2 particles include minerals which are isotopically and mineralogically similar to CAIs [e.g., 2, 3] and chondrules [e.g., 4] in chondrites. In addition, particles similar to amoeboid olivine aggregates (AOAs) also have been discovered [5, 6,7]. C2067,2,112,1 is a terminal particle recovered from track #112 (T112). Nakamura-Messenger et al. [7] showed that the forsterite grain in T112 has O-16 enrichment of approximately 40 0/00 (vs. SMOW) and possibly formed together with AOAs. In this study, we have examined the mineralogy of the T112 particle and compared the possible relationships between T112 and AOAs in primitive meteorites.

Komatsu, M.↗

A Coordinated Focused Ion Beam/Ultramicrotomy Technique for Serial Sectioning of Hayabusa Particles and Other Returned Samples

Recent sample return missions, such as NASA's Stardust mission to comet 81P/Wild 2 and JAXA's Hayabusa mission to asteroid 25143 Itokawa, have returned particulate samples (typically ~5-50 μm) that pose tremendous challenges to coordinated analysis using a variety of nano- and micro-beam techniques. The ability to glean maximal information from individual particles has become increasingly important and depends critically on how the samples are prepared for analysis. This also holds true for other extraterrestrial materials, including interplanetary dust particles, micrometeorites and lunar regolith grains. Traditionally, particulate samples have been prepared using microtomy techniques (e.g., [1]). However, for hard mineral particles ≳20 μm, microtome thin sections are compromised by severe chatter and sample loss. For these difficult samples, we have developed a hybrid technique that combines traditional ultramicrotomy with focused ion beam (FIB) techniques, allowing for the in situ investigation of grain surfaces and interiors. Using this method, we have increased the number of FIB-SEM prepared sections that can be recovered from a particle with dimensions on the order of tens of μms. These sections can be subsequently analyzed using a variety of electron beam techniques. Here, we demonstrate this sample preparation technique on individual lunar regolith grains in order to study their space-weathered surfaces. We plan to extend these efforts to analyses of individual Hayabusa samples.

Berger, E. L.↗

Curation and Analysis of Samples from Comet Wild-2 Returned by NASA's Stardust Mission

The NASA Stardust mission returned the first direct samples of a cometary coma from comet 81P/Wild‐2 in 2006. Intact capture of samples encountered at 6 km/s was enabled by the use of aerogel, an ultralow dense silica polymer. Approximately 1000 particles were captured, with micron and submicron materials distributed along ~mm scale length tracks. This sample collection method and the fine scale of the samples posed new challenges to the curation and cosmochemistry communities. Sample curation involved extensive, detailed photo‐documentation and delicate micro‐surgery to remove particles without loss from the aerogel tracks. This work had to be performed in highly clean facility to minimize the potential of contamination. JSC Curation provided samples ranging from entire tracks to micrometer‐sized particles to external investigators. From the analysis perspective, distinguishing cometary materials from aerogel and identifying the potential alteration from the capture process were essential. Here, transmission electron microscopy (TEM) proved to be the key technique that would make this possible. Based on TEM work by ourselves and others, a variety of surprising findings were reported, such as the observation of high temperature phases resembling those found in meteorites, rarely intact presolar grains and scarce organic grains and submicrometer silicates. An important lesson from this experience is that curation and analysis teams must work closely together to understand the requirements and challenges of each task. The Stardust Mission also has laid important foundation to future sample returns including OSIRIS‐REx and Hayabusa II and future cometary nucleus sample return missions.

Nakamura-Messenger, Keiko↗

Nebular and Interstellar Materials in a Giant Cluster IDP of Probable Cometary Origin

Comets contain a complex mixture of materials with presolar and Solar System origins. Chondritic porous interplanetary dust particles (CP-IDPs) are associated with comets by their fragile nature, unequilibrated anhydrous mineralogy and high abundances of circumstellar grains and isotopically anomalous organic materials. Comet 81P/Wild 2 samples returned by the Stardust spacecraft contain presolar materials as well as refractory 16O-rich Ca-Al-rich inclusion- (CAI), chondrule-, and AOA-like materials. We are conducting coordinated chemical, mineralogical, and isotopic studies of a giant cluster CP-IDP (U2-20-GCA) to determine the proportions of inner Solar System and interstellar materials. We previously found that this IDP contains abundant presolar silicates (approx. 1,800 ppm) and 15N-rich hotspots [6].

Messenger, S.↗

Advances in Small Particle Handling of Astromaterials in Preparation for OSIRIS-REx and Hayabusa2: Initial Developments

The Astromaterials Acquisition and Curation office at NASA Johnson Space Center has established an Advanced Curation program that is tasked with developing procedures, technologies, and data sets necessary for the curation of future astromaterials collections as envisioned by NASA exploration goals. One particular objective of the Advanced Curation program is the development of new methods for the collection, storage, handling and characterization of small (less than 100 micrometer) particles. Astromaterials Curation currently maintains four small particle collections: Cosmic Dust that has been collected in Earth's stratosphere by ER2 and WB-57 aircraft, Comet 81P/Wild 2 dust returned by NASA's Stardust spacecraft, interstellar dust that was returned by Stardust, and asteroid Itokawa particles that were returned by the JAXA's Hayabusa spacecraft. NASA Curation is currently preparing for the anticipated return of two new astromaterials collections - asteroid Ryugu regolith to be collected by Hayabusa2 spacecraft in 2021 (samples will be provided by JAXA as part of an international agreement), and asteroid Bennu regolith to be collected by the OSIRIS-REx spacecraft and returned in 2023. A substantial portion of these returned samples are expected to consist of small particle components, and mission requirements necessitate the development of new processing tools and methods in order to maximize the scientific yield from these valuable acquisitions. Here we describe initial progress towards the development of applicable sample handling methods for the successful curation of future small particle collections.

Snead, C. J.↗

Advanced Curation Development of Tools and Methods for Microparticle Curation

The Astromaterials Acquisition and Curation Office at NASA Johnson Space Center is currently developing new tools and methods for the collection, storage, handling and characterization of particles less than 100 microns in diameter, or microparticles. Astromaterials Curation currently maintains four microparticle collections: Cosmic Dust that has been collected in Earth’s stratosphere by ER2 and WB-57 aircraft, Comet 81P/Wild 2 dust returned by NASA’s Stardust spacecraft, interstellar dust that was returned by Stardust, and asteroid Itokawa particles that were returned by the JAXA (Japan Aerospace Exploration Agency)’s Hayabusa spacecraft. NASA Curation is currently preparing for the anticipated return of two new astromaterials collections – asteroid Ryugu regolith to be collected by Hayabusa II spacecraft in 2021 (samples will be provided by JAXA as part of an international agreement), and asteroid Bennu regolith to be collected by the OSIRIS-REx (Origins Spectral Interpretation Resource Identification Security - Regolith Explorer) spacecraft in 2023. In order to maximize the scientific yield from these valuable acquisitions, it will be necessary to develop methods that extend our current microsample handling capabilities. Here we describe recent progress in the development of sample handling techniques that will enhance our microparticle curation capabilities. Further described are: Six-Axis Robot Arms for Particle Manipulation, and Charge-Dissipative Substrates.

Snead, Christopher↗

An Improved Hf Vapor Etching Apparatus for Stardust Particle Extraction

Introduction: The NASA Stardust mission captured thousands of particles from the Jupiter-family comet 81P/Wild 2 in a collector composed of aluminum foil and blocks of silica aerogel [1]. To date, most Wild 2 particles available for study are relatively large and coherent particles extracted individually from the ends of hollow, carrot-shaped impact tracks produced during impact into aerogel. However, >65% of the impacting mass can be found in the ‘bulb’ of the track, including nearly all of the <1 μm size fraction [2]. This fraction contains organic-rich material and is likely to include presolar grains, representing a critical opportunity to constrain the organic and presolar inventory of primitive outer solar system materials. However, the small size and susceptibility of this fraction to melting or alteration during capture poses significant analytical challenges. Previous attempts to extract and concentrate fine-grained material from the bulb of Stardust tracks have attempted to develop techniques that efficiently destroy aerogel and leave impactor particles relatively unharmed. The low density and high porosity of silica aerogel makes it more susceptible to attack by etching with hydrofluoric acid (HF) [3] or CF4 plasma ashing [4] than collected cometary silicates. Previous studies of HF vapor etching used HF solutions varying between 5 to 49% and noted that at high concentrations and etch rates, a liquid droplet was produced according to the etching reaction 4HF + SiO2 → SiF4 (g) + 2H2O [3]. SiF4 readily decomposes into HF and silicic acid in water, which has the potential to alter the freed cometary silicates. The plasma ashing technique avoids production of a liquid droplet and minimizes damage to embedded silicates but requires specialized equipment [4]. In this abstract, we present recent improvements to the HF etching procedure with the aim of constructing an etching chamber capable of slowly etching silica aerogel using small quantities of dilute HF. The etching chamber can be assembled using readily available materials.

Stardust↗

HF Vapor Etching for Stardust Particle Extraction: A Progress Report

The Stardust mission captured thousands of particles from Jupiter-family comet 81P/Wild 2 using aluminum foil and silica aerogel collection media [1]. Most studies of Wild 2 material examine refractory terminal particles >1 μm in diameter which are extracted individually from the ends of tracks produced by the particle’s impact into the aerogel medium. A substantial (>65 %) mass fraction of the impactors is present as fine-grained (i.e. <1 μm) material in the ‘bulb’ and walls of the tracks, which may contain preserved organic material and presolar grains [2]. Few presolar grains have been identified in Stardust samples, which has been interpreted as owing to destruction upon impact into the foils and preferential sampling of terminal particles rather than a lack of presolar grains in Wild 2 samples [3-5]. By isolating the fine-grained material from these bulbs and performing microbeam and isotopic analyses (i.e., scanning electron microscopy and NanoSIMS), organic matter and presolar grains can be identified and constraints can be placed on the constituents of primitive outer solar system materials.

Stardust↗

The Diversity of Refractory Organic Material in Comets

Organic matter exists in comets (most notably in 81P/Wild 2 [Stardust], 67P/Churyomov- Gerasimenko (67P/C-G) [Rosetta], chondritic porous IDPS, and UCAMMs) and in primitive carbonaceous chondrites that likely retain some chemistry that reflects an origin in the prenatal cold molecular cloud (Alexander+2017). Heavy isotopic enrichments, 15N/14N and possibly D/H, signify preserved molecular cloud organics. In the cold outer disk, if grains are lofted above the disk mid-plane then organics likely experience significant UV processing (Ciesla+2012). In remote sensing of comet comae, organics in the dust are considered refractory or semirefractory. Semi-refractory organics have limited comae lifetimes and produce distributed sources of molecules (H2CO and CO). Rosetta's close passes of 67P/C-G's nucleus (10-15 km) reveals a distributed source of glycine, methyl amine and ethylamine (Altwegg+2016). Cometary samples and primitive meteorites have two types of organic matter: (1) acid-insoluble organic matter (IOM), which is a macromolecular polymer with a mixture of aromatic and aliphatic moieties, and (2) labile, soluble organics, which includes the amino acids, such as glycine (Stardust, Elsila+2009). Meteoritic IOM is robust, withstanding experimental temperatures of 1200 K (Dobrica+2011, Cody+2008). Nanoglobules are a type of IOM; they have a distinct physical structure, but often share the same chemistry as the other IOM from the same meteorite. Moderate-sized PAHs (20 C-atoms) are detected in Stardust samples (Clemett+2010). Refractory organic IOM is ubiquitous yet has a great diversity of abundances between cometary samples. IOM is in primitive chondrites, 67P/C-G (Rosetta), 81P/Wild 2 (Stardust), 1P/Halley, 26P/Grigg-Skjellerup, UCAMMs, anhydrous IDPs, and in chondritic porous IDPs (CP IDPs) and larger cluster IDPs (e.g., Fray+2016, Fomenkova+94, Busemann+ 09, Dobrica+2011, Dobrica+2012). 81P's refractory organic matter is of two types (De Gregorio+2011): nanoglobules of highly aromatic refractory organic matter and polyaromatic carbonyl-containing organic matter, which is similar to IOM in primitive meteorites and IDPs. Fray+2017 estimate that 50% of carbon in 67P/C-G is in IOM. 67P/C-G's organics appear to lack the soluble organic matter, aliphatic carbon, amino acids, and PAHs (Fray+2016). Other notable aspects of the diversity in IOM in cometary samples are the ranges of atomic ratios of N/C, O/C, and H/C, and the range of isotopic enrichments of 15N/14N and D/H. Aqueous and thermal processing on asteroids changes the balance of soluble to insoluble organics, and may be important for diversifying the range of OM delivered to Earth.

Wooden, Diane↗

Characterization of 81P/Wild 2 Particles C2067,1,111,6.0 and C2067,1,111,8.0

The concentrations of C and N in cometary particles are of interest in characterizing the regions where comets formed. One aim of this work is to analyze enough Stardust particles to draw meaningful statistical conclusions about their inventories of C and N. Toward that end we report recent studies of Stardust particles and related materials.

Smith, T.↗

Stardust Sample Collection at Wild 2 and Its Preliminary Examination

The primary objective of STARDUST is to collect coma samples from 81P/Wild 2. This was made on January 2, 2004. Before the encounter three significant model predictions existed for the number and size of samples to be captured. Three investigations during the Wild 2 encounter (Dust Flux Monitor, Comet and Interstellar Dust Analyzer and Dynamic Science) made in situ measurements of the dust. Spectacular images were captured of the Wild 2 nucleus and dust jets. This abstract compares the model predictions with the in situ measurements and Wild 2 images and assesses the likely samples to be returned for analysis on January 15, 2006. To give some lead time for sample analysts to prepare for the analyses of the returned samples, the organization of the Preliminary Examination is presented.

Tsou, P.↗

Characterization of Three Carbon- and Nitrogen-Rich Particles from Comet 81P/WILD

Comets may sample the early solar system s complement of volatile-forming elements - including C and N - more fully and reliably than do the terrestrial planets or asteroids. Until recently, all elemental analyses of unambiguously cometary material were carried out remotely. The return of the Stardust mission makes it possible to analyze documented material from P81/Wild 2 in the laboratory Wild 2 particles fragmented when they stopped in the aerogel collectors. We have studied three fragments thought to be rich in C and N by using several techniques: FTIR to characterize organic matter; synchrotron-induced x-ray fluorescence (SXRF) to determine Fe and certain element/Fe ratios; SEM to image sample morphology and to detect semiquantitatively Mg, Al, Si, Ca, and Fe; and nuclear reaction analysis (NRA) to measure C, N, O, and Si.

Gallien, J.-P.↗

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↗