Organic compound alteration during hypervelocity collection of carbonaceous materials in aerogel

Abstract— The NASA Stardust mission brought to Earth micron‐size particles from the coma of comet 81P/Wild 2 using aerogel, a porous silica material, as the capture medium. A major challenge in understanding the organic inventory of the returned comet dust is identifying, unambiguously, which organic molecules are indigenous to the cometary particles, which are produced from carbon contamination in the Stardust aerogel, and which are cometary organics that have been modified by heating during the particle capture process. Here it is shown that 1) alteration of cometary organic molecules along impact tracks in aerogel is highly dependent on the original particle morphology, and 2) organic molecules on test‐shot terminal particles are mostly preserved. These conclusions are based on two‐step laser mass spectrometry (L²MS) examinations of test shots with organic‐laden particles (both tracks in aerogel and the terminal particles themselves).     

FIB‐TEM analysis of cometary material in 10 Stardust foil craters

Aluminum foils from the Stardust cometary dust collector contain impact craters formed during the spacecraft's encounter with comet 81P/Wild 2 and retain residues that are among the few unambiguously cometary samples available for laboratory study. Our study investigates four micron‐scale (1.8–5.2 μm) and six submicron (220–380 nm) diameter craters to better characterize the fine (<1 μm) component of comet Wild 2. We perform initial crater identification with scanning electron microscopy, prepare the samples for further analysis with a focused ion beam, and analyze the cross sections of the impact craters with transmission electron microscopy (TEM). All of the craters are dominated by combinations of silicate and iron sulfide residues. Two micron‐scale craters had subregions that are consistent with spinel and taenite impactors, indicating that the micron‐scale craters have a refractory component. Four submicron craters contained amorphous residue layers composed of silicate and sulfide impactors. The lack of refractory materials in the submicron craters suggests that refractory material abundances may differentiate Wild 2 dust on the scale of several hundred nanometers from larger particles on the scale of a micron. The submicron craters are enriched in moderately volatile elements (S, Zn) when normalized to Si and CI chondrite abundances, suggesting that, if these craters are representative of the Wild 2 fine component, the Wild 2 fines were not formed by high‐temperature condensation. This distinguishes the comet's fine component from the large terminal particles in Stardust aerogel tracks which mostly formed in high‐temperature events.     

Aerogel tracks made by impacts of glycine: Implications for formation of bulbous tracks in aerogel and the Stardust mission

Abstract– Impacts of small particles of soda‐lime glass and glycine onto low density aerogel are reported. The aerogel had a quality similar to the flight aerogels carried by the NASA Stardust mission that collected cometary dust during a flyby of comet 81P/Wild 2 in 2004. The types of track formed in the aerogel by the impacts of the soda‐lime glass and glycine are shown to be different, both qualitatively and quantitatively. For example, the soda‐lime glass tracks have a carrot‐like appearance and are relatively long and slender (width to length ratio <0.11), whereas the glycine tracks consist of bulbous cavities (width to length ratio >0.26). In consequence, the glycine particles would be underestimated in diameter by a factor of 1.7–3.2, if the glycine tracks were analyzed using the soda‐lime glass calibration and density. This implies that a single calibration for impacting particle size based on track properties, as previously used by Stardust to obtain cometary dust particle size, is inappropriate.     

Interpretation of Wild 2 dust fine structure: Comparison of Stardust aluminum foil craters to the three‐dimensional shape of experimental impacts by artificial aggregate particles and meteorite powders

Abstract— New experimental results show that Stardust crater morphology is consistent with interpretation of many larger Wild 2 dust grains being aggregates, albeit most of low porosity and therefore relatively high density. The majority of large Stardust grains (i.e. those carrying most of the cometary dust mass) probably had density of 2.4 g cm^?3 (similar to soda‐lime glass used in earlier calibration experiments) or greater, and porosity of 25% or less, akin to consolidated carbonaceous chondrite meteorites, and much lower than the 80% suggested for fractal dust aggregates. Although better size calibration is required for interpretation of the very smallest impacting grains, we suggest that aggregates could have dense components dominated by μm‐scale and smaller sub‐grains. If porosity of the Wild 2 nucleus is high, with similar bulk density to other comets, much of the pore space may be at a scale of tens of micrometers, between coarser, denser grains. Successful demonstration of aggregate projectile impacts in the laboratory now opens the possibility of experiments to further constrain the conditions for creation of bulbous (Type C) tracks in aerogel, which we have observed in recent shots. We are also using mixed mineral aggregates to document differential survival of pristine composition and crystalline structure in diverse finegrained components of aggregate cometary dust analogues, impacted onto both foil and aerogel under Stardust encounter conditions.     

Physical, Chemical, and Mineralogical Properties of Comet 81P/Wild 2 Particles Collected by Stardust

NASA’s Stardust spacecraft collected dust from the coma of Comet 81P/Wild 2 by impact into aerogel capture cells or into Al-foils. The first direct, laboratory measurement of the physical, chemical, and mineralogical properties of cometary dust grains ranging from <10⁻¹⁵ to ∼10⁻⁴ g were made on this dust. Deposition of material along the entry tracks in aerogel and the presence of compound craters in the Al-foils both indicate that many of the Wild 2 particles in the size range sampled by Stardust are weakly bound aggregates of a diverse range of minerals. Mineralogical characterization of fragments extracted from tracks indicates that most tracks were dominated by olivine, low-Ca pyroxene, or Fe-sulfides, although one track was dominated by refractory minerals similar to Ca–Al inclusions in primitive meteorites. Minor mineral phases, including Cu–Fe-sulfide, Fe–Zn-sulfide, carbonate and metal oxides, were found along some tracks. The high degree of variability of the element/Fe ratios for S, Ca, Ti, Cr, Mn, Ni, Cu, Zn, and Ga among the 23 tracks from aerogel capture cells analyzed during Stardust Preliminary Examination is consistent with the mineralogical variability. This indicates Wild 2 particles have widely varying compositions at the largest size analyzed (>10 μm). Because Stardust collected particles from several jets, sampling material from different regions of the interior of Wild 2, these particles are expected to be representative of the non-volatile component of the comet over the size range sampled. Thus, the stream of particles associated with Comet Wild 2 contains individual grains of diverse elemental and mineralogical compositions, some rich in Fe and S, some in Mg, and others in Ca and Al. The mean refractory element abundance pattern in the Wild 2 particles that were examined is consistent with the CI meteorite pattern for Mg, Si, Cr, Fe, and Ni to 35%, and for Ca, Ti and Mn to 60%, but S/Si and Fe/Si both show a statistically significant depletion from the CI values and the moderately volatile elements Cu, Zn, Ga are enriched relative to CI. This elemental abundance pattern is similar to that in anhydrous, porous interplanetary dust particles (IDPs), suggesting that, if Wild 2 dust preserves the original composition of the Solar Nebula, the anhydrous, porous IDPs, not the CI meteorites, may best reflect the Solar Nebula abundances. This might be tested by elemental composition measurements on cometary meteors.     

Infrared spectroscopy of Wild 2 particle hypervelocity tracks in Stardust aerogel: Evidence for the presence of volatile organics in cometary dust

Abstract— Infrared spectroscopy maps of some tracks made by cometary dust from 81P/Wild 2 impacting Stardust aerogel reveal an interesting distribution of organic material. Out of six examined tracks, three show presence of volatile organic components possibly injected into the aerogel during particle impacts. When particle tracks contained volatile organic material, they were found to be ‐CH₂‐rich, while the aerogel is dominated by the ‐CH₃‐rich contaminant. It is clear that the population of cometary particles impacting the Stardust aerogel collectors also includes grains that contained little or none of this organic component. This observation is consistent with the highly heterogeneous nature of collected grains, as seen by a multitude of other analytical techniques.     

Dust in cometary comae: Present understanding of the structure and composition of dust particles

In situ probing of a very few cometary comae has shown that dust particles present a low albedo and a low density, and that they consist of both rocky material and refractory organics. Remote observations of solar light scattered by cometary dust provide information on the properties of dust particles in the coma of a larger set of comets. The observations of the linear polarization in the coma indicate that the dust particles are irregular, with a size greater (on the average) than about 1 μm. Besides, they suggest, through numerical and experimental simulations, that both compact grains and fluffy aggregates (with a power law of the size distribution in the −2.6 to −3 range), and both rather transparent silicates and absorbing organics are present in the coma. Recent analysis of the cometary dust samples collected by the Stardust mission provide a unique ground truth and confirm, for comet 81P/Wild 2, the results from remote sensing observations. Future space missions to comets should, in the next decade, lead to a more precise characterization of the structure and composition of cometary dust particles.     

Analytical scanning and transmission electron microscopy of laboratory impacts on Stardust aluminum foils: Interpreting impact crater morphology and the composition of impact residues

Abstract— The known encounter velocity (6.1 kms^?1) and particle incidence angle (perpendicular) between the Stardust spacecraft and the dust emanating from the nucleus of comet Wild‐2 fall within a range that allows simulation in laboratory light‐gas gun (LGG) experiments designed to validate analytical methods for the interpretation of dust impacts on the aluminum foil components of the Stardust collector. Buckshot of a wide size, shape, and density range of mineral, glass, polymer, and metal grains, have been fired to impact perpendicularly on samples of Stardust Al 1100 foil, tightly wrapped onto aluminum alloy plate as an analogue of foil on the spacecraft collector. We have not yet been able to produce laboratory impacts by projectiles with weak and porous aggregate structure, as may occur in some cometary dust grains. In this report we present information on crater gross morphology and its dependence on particle size and density, the pre‐existing major‐ and trace‐element composition of the foil, geometrical issues for energy dispersive X‐ray analysis of the impact residues in scanning electron microscopes, and the modification of dust chemical composition during creation of impact craters as revealed by analytical transmission electron microscopy. Together, these observations help to underpin the interpretation of size, density, and composition for particles impacted on the Stardust aluminum foils.     

Capture effects in carbonaceous material: A Stardust analogue study

Abstract— It is reasonable to expect that cometary samples returned to Earth by the Stardust space probe have been altered to some degree during capture in aerogel at 6.1 km/s. In order to help interpret the measured structure of these particles with respect to their original cometary nature, a series of coal samples of known structure and chemical composition was fired into aerogel at Stardust capture velocity. This portion of the study analyzed the surfaces of aerogel‐embedded particles using Raman spectroscopy. Results show that particle surfaces are largely homogenized during capture regardless of metamorphic grade or chemical composition, apparently to include a devolatilization step during capture processing. This provides a possible mechanism for alteration of some aliphatic compound‐rich phases through devolatilization of cometary carbonaceous material followed by re‐condensation within the particle. Results also show that the possibility of alteration must be considered for any particular Stardust grain, as examples of both graphitization and amorphization are found in the coal samples. It is evident that Raman G band (～1580 cm^?1) parameters provide a means of characterizing Stardust carbonaceous material to include identifying those grains which have been subjected to significant capture alteration.     

Connection between micrometeorites and Wild 2 particles: From Antarctic snow to cometary ices

Abstract— We discuss the relationship between large cosmic dust that represents the main source of extraterrestrial matter presently accreted by the Earth and samples from comet 81P/Wild 2 returned by the Stardust mission in January 2006. Prior examinations of the Stardust samples have shown that Wild 2 cometary dust particles contain a large diversity of components, formed at various heliocentric distances. These analyses suggest large‐scale radial mixing mechanism(s) in the early solar nebula and the existence of a continuum between primitive asteroidal and cometary matter. The recent collection of CONCORDIA Antarctic micrometeorites recovered from ultra‐clean snow close to Dome C provides the most unbiased collection of large cosmic dust available for analyses in the laboratory. Many similarities can be found between Antarctic micrometeorites and Wild 2 samples, in terms of chemical, mineralogical, and isotopic compositions, and in the structure and composition of their carbonaceous matter. Cosmic dust in the form of CONCORDIA Antarctic micrometeorites and primitive IDPs are preferred samples to study the asteroid‐comet continuum.     

Oxygen isotopic composition of an enstatite ribbon of probable cometary origin

Filamentary enstatite crystals are found in interplanetary dust particles (IDPs) of likely cometary origin but are very rare or absent in meteorites. Crystallographic characteristics of filamentary enstatites indicate that they condensed directly from vapor. We measured the O isotopic composition of an enstatite ribbon from a giant cluster IDP to be δ¹⁸O = 25 ± 55, δ¹⁷O = ?19 ± 129, ?¹⁷O = ?32 ± 134 (2σ errors), which is inconsistent at the 2σ level with the composition of the Sun inferred from the Genesis solar wind measurements. The particle's O isotopic composition, consistent with the terrestrial composition, implies that it condensed from a gas of nonsolar O isotopic composition, possibly as a result of vaporization of disk region enriched in ¹⁶O‐depleted solids. The relative scarcity of filamentary enstatite in asteroids compared to comets implies either that this crystal condensed from dust vaporized in situ in the outer solar system where comets formed or it condensed in the inner solar system and was subsequently transported outward to the comet‐forming region.     

Organic and inorganic correlations for Northwest Africa 852 by synchrotron‐based Fourier transform infrared microspectroscopy

Relationships between organic molecules and inorganic minerals are investigated in a single 34 μm diameter grain of the CR2 chondrite Northwest Africa 852 (NWA) 852 with submicron spatial resolution using synchrotron‐based imaging micro‐FTIR spectroscopy. Correlations based on absorption strength for the various constituents are determined using statistical correlation analysis. The silicate band is found to be correlated with the hydration band, and the latter is highly correlated with stretching modes of aliphatic hydrocarbons. Spatial distribution maps show that water+organic combination, silicate, OH, and C‐H distributions overlap, suggesting a possible catalytic role of phyllosilicates in the formation of organics. In contrast, the carbonate band is anticorrelated with water+organic combination, however uncorrelated with any other spectral feature. The average ratio of asymmetric CH₂ and CH₃ band strengths (CH₂/CH₃ = 2.53) for NWA 852 is similar to the average ratio of interplanetary dust particles (~2.40) and Wild 2 cometary dust particles (2.50), but it significantly exceeds that of interstellar medium objects (~1.00) and several aqueously altered carbonaceous chondrites (~1.40). This suggests organics of similar length/branching, and perhaps similar formation regions, for NWA 852, Wild 2 dust particles, and interplanetary dust particles. The heterogeneous spatial distribution of ratio values indicates the presence of a mixture of aliphatic organic material with different length/branching, and thus a wide range of parent body processes, which occurred before the considered grain was formed.     

Prediction of the in-situ dust measurements of the stardust mission to comet 81P⧸Wild 2

We predict the amount of cometary, interplanetary, and interstellar cosmic dust that is to be measured by the Cometary and Interstellar Dust Analyzer (CIDA) and the aerogel collector on board the Stardust spacecraft during its fly-by of comet P⧸Wild 2 and during the interplanetary cruise phase. We give the dust flux on the spacecraft during the encounter with the comet using both, a radially symmetric and an axially symmetric coma model. At closest approach, we predict a total dust flux of 10⁶⁰ m⁻² s⁻¹ for the radially symmetric case and 10⁶⁵ m⁻² s⁻¹ for the axially symmetric case. This prediction is based on an observation of the comet at a heliocentric distance of 1.7 AU. We reproduce the measurements of the Giotto and VEGA missions to comet P⧸Halley using the same model as for the Stardust predictions. The planned measurements of interstellar dust by Stardust have been triggered by the discovery of interstellar dust impacts in the data collected by the Ulysses and Galileo dust detector. Using the Ulysses and Galileo measurements we predict that 25 interstellar particles, mainly with masses of about 10⁻¹² g, will hit the target of the CIDA experiment. The interstellar side of the aerogel collector will contain 120 interstellar particles, 40 of which with sizes greater than 1 μm. Furthermore, we investigate the contamination of the CIDA and collector measurements by interplanetary particles during the cruise phase.     

Extent of thermal ablation suffered by model organic microparticles during aerogel capture at hypervelocities

Abstract— New model organic microparticles are used to assess the thermal ablation that occurs during aerogel capture at speeds from 1 to 6 km s^?1. Commercial polystyrene particles (20 μm diameter) were coated with an ultrathin 20 nm overlayer of an organic conducting polymer, polypyrrole. This overlayer comprises only 0.8% by mass of the projectile but has a very strong Raman signature, hence its survival or destruction is a sensitive measure of the extent of chemical degradation suffered. After aerogel capture, microparticles were located via optical microscopy and their composition was analyzed in situ using Raman microscopy. The ultrathin polypyrrole overlayer survived essentially intact for impacts at ～1 km s^?1, but significant surface carbonization was found at 2 km s^?1, and major particle mass loss at ≥3 km s^?1. Particles impacting at ～6.1 km s^?1 (the speed at which cometary dust was collected in the NASA Stardust mission) were reduced to approximately half their original diameter during aerogel capture (i.e., a mass loss of 84%). Thus significant thermal ablation occurs at speeds above a few km s^?1. This suggests that during the Stardust mission the thermal history of the terminal dust grains during capture in aerogel may be sufficient to cause significant processing or loss of organic materials. Further, while Raman D and G bands of carbon can be obtained from captured grains, they may well reflect the thermal processing during capture rather than the pre‐impact particle's thermal history.     

Exposure and analysis of microparticles embedded in silica aerogel keystones using NF3‐mediated electron beam–induced etching and energy‐dispersive X‐ray spectroscopy

In 2006, NASA's Stardust spacecraft delivered to Earth dust particles collected from the coma of comet 81P/Wild 2, with the goal of furthering the understanding of solar system formation. Stardust cometary samples were collected in a low‐density, nanoporous silica aerogel making their study technically challenging. This article demonstrates the identification, exposure, and elemental composition analysis of particles analogous to those collected by NASA's Stardust mission using in‐situ SEM techniques. Backscattered electron imaging is shown by experimental observation and Monte Carlo simulation to be suitable for locating particles of a range of sizes relevant to Stardust (down to submicron diameters) embedded within silica aerogel. Selective removal of the silica aerogel encapsulating an embedded particle is performed by cryogenic NF₃‐mediated electron beam–induced etching. The porous, low‐density nature of the aerogel results in an enhanced etch rate compared with solid material, making it an effective, nonmechanical method for the exposure of particles. After exposure, elemental composition of the particle was analyzed by energy‐dispersive X‐ray spectroscopy using a high spectral resolution microcalorimeter. Signals from fluorine contamination are shown to correspond to nonremoved silica aerogel and only in residual concentrations.     

Magnetite in Comet Wild 2: Evidence for parent body aqueous alteration

The mineralogy of comet 81P/Wild 2 particles, collected in aerogel by the Stardust mission, has been determined using synchrotron Fe‐K X‐ray absorption spectroscopy with in situ transmission XRD and X‐ray fluorescence, plus complementary microRaman analyses. Our investigation focuses on the terminal grains of eight Stardust tracks: C2112,4,170,0,0; C2045,2,176,0,0; C2045,3,177,0,0; C2045,4,178,0,0; C2065,4,187,0,0; C2098,4,188,0,0; C2119,4,189,0,0; and C2119,5,190,0,0. Three terminal grains have been identified as near pure magnetite Fe₃O₄. The presence of magnetite shows affinities between the Wild 2 mineral assemblage and carbonaceous chondrites, and probably resulted from hydrothermal alteration of the coexisting FeNi and ferromagnesian silicates in the cometary parent body. In order to further explore this hypothesis, powdered material from a CR2 meteorite (NWA 10256) was shot into the aerogel at 6.1 km s^?1, using a light‐gas gun, and keystones were then prepared in the same way as the Stardust keystones. Using similar analysis techniques to the eight Stardust tracks, a CR2 magnetite terminal grain establishes the likelihood of preserving magnetite during capture in silica aerogel.     

Comparison of GEMS in interplanetary dust particles and GEMS‐like objects in a Stardust impact track in aerogel

Comet 81P/Wild 2 dust, the first comet sample of known provenance, was widely expected to resemble anhydrous chondritic porous (CP) interplanetary dust particles (IDPs). GEMS, distinctly characteristic of CP IDPs, have yet to be unambiguously identified in the Stardust mission samples despite claims of likely candidates. One such candidate is Stardust impact track 57 “Febo” in aerogel, which contains fine‐grained objects texturally and compositionally similar to GEMS. Their position adjacent the terminal particle suggests that they may be indigenous, fine‐grained, cometary material, like that in CP IDPs, shielded by the terminal particle from damage during deceleration from hypervelocity. Dark‐field imaging and multidetector energy‐dispersive X‐ray mapping were used to compare GEMS‐like‐objects in the Febo terminal particle with GEMS in an anhydrous, chondritic IDP. GEMS in the IDP are within 3× CI (solar) abundances for major and minor elements. In the Febo GEMS‐like objects, Mg and Ca are systematically and strongly depleted relative to CI; S and Fe are somewhat enriched; and Au, a known aerogel contaminant, is present, consistent with ablation, melting, abrasion, and mixing of the SiO_x aerogel with crystalline Fe‐sulfide and minor enstatite, high‐Ni sulfide, and augite identified by elemental mapping in the terminal particle. Thus, GEMS‐like objects in “caches” of fine‐grained debris abutting terminal particles are most likely deceleration debris packed in place during particle transit through the aerogel.     

Searching for calcium‐aluminum‐rich inclusions in cometary particles with Rosetta/COSIMA

The calcium‐aluminum‐rich inclusions (CAIs) found in chondritic meteorites are probably the oldest solar system solids, dating back to 4567.30 ± 0.16 million years ago. They are thought to have formed in the protosolar nebula within a few astronomical units of the Sun, and at a temperature of around 1300 K. The Stardust mission found evidence of CAI‐like material in samples recovered from comet Wild 2. The appearance of CAIs in comets, which are thought to be formed at lower temperatures and larger distances from the Sun, is only explicable if some mechanism allows the efficient transfer of such objects from the inner solar nebula to the outer solar nebula. Such mechanisms have been proposed such as an X‐wind or turbulence. In this work, particles collected from within the coma of comet 67P/Churyumov–Gerasimenko are examined for compositional evidence of the presence of CAIs. COSIMA (the Cometary Secondary Ion Mass Analyzer) uses secondary ion mass spectrometry to analyze the composition of cometary dust captured on metal targets. While CAIs can have a radius of centimeters, they are more typically a few hundred microns in size, and can be smaller than 1 μm, so it is conceivable that particles visible on COSIMA targets (ranging in size from about 10 μm to hundreds of microns) could contain CAIs. Using a peak fitting technique, the composition of a set of 13 particles was studied, looking for material rich in both calcium and aluminum. One such particle was found.     

Cover

Cover: Light microscope image of 950 μm‐long Stardust track, C2045,4,178,0,0 (#178), of cometary grains captured in aerogel at 6.1 kms^‐1. Hicks et al. discuss the identifi cation of magnetite in this and other Stardust tracks. The magnetite is interpreted to have formed through water‐rock reaction on the comet Wild 2 parent body. Scale bar = 200 μm. Image courtesy of L. Hicks.     

High precision oxygen three‐isotope analyses of anhydrous chondritic interplanetary dust particles

Abstract– Oxygen three‐isotope ratios of three anhydrous chondritic interplanetary dust particles (IDPs) were analyzed using an ion microprobe with a 2 μm small beam. The three anhydrous IDPs show Δ¹⁷O values ranging from ?5‰ to +1‰, which overlap with those of ferromagnesian silicate particles from comet Wild 2 and anhydrous porous IDPs. For the first time, internal oxygen isotope heterogeneity was resolved in two IDPs at the level of a few per mil in Δ¹⁷O values. Anhydrous IDPs are loose aggregates of fine‐grained silicates (≤3 μm in this study), with only a few coarse‐grained silicates (2–20 μm in this study). On the other hand, Wild 2 particles analyzed so far show relatively coarse‐grained (≥ few μm) igneous textures. If anhydrous IDPs represent fine‐grained particles from comets, the similar Δ¹⁷O values between anhydrous IDPs and Wild 2 particles may imply that oxygen isotope ratios in cometary crystalline silicates are similar, independent of crystal sizes and their textures. The range of Δ¹⁷O values of the three anhydrous IDPs overlaps also with that of chondrules in carbonaceous chondrites, suggesting a genetic link between cometary dust particles (Wild 2 particles and most anhydrous IDPs) and carbonaceous chondrite chondrules.