Acrylic embedding of Stardust particles encased in aerogel

Abstract— Ultramicrotomy of samples embedded in epoxy resin is a standard method for preparing ultra‐thin sections for electron microscopy. In this report we describe a new embedding technique that uses acrylic resin instead of epoxy. This method offers several important advantages for sectioning small extraterrestrial samples. One is that the acrylic resin is soluble and can be removed after ultramicrotomy to leave a sample that is free of the mounting media. This is important for studying carbon and insoluble organic components. A second major advantage of acrylic is that, when combined with pre‐embedding compression, it provides a very effective method of mounting samples collected in silica aerogel. Acrylic embedding is currently being used to mount comet particles collected by NASA's Stardust mission. Combined with a flattening process, the acrylic embedding and sectioning preserves all pieces of collected samples in their collection matrix. In addition to Stardust, acrylic may be applied to other samples collected in aerogel such as those from the Russian Mir space station (Hörz et al. 2000) and future missions such as Sample Collection for Investigation of Mars (SCIM) (Leshin 2003), a proposed mission to collect atmospheric dust particles from Mars.     

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.     

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.     

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.     

A refractory inclusion returned by Stardust from comet 81P/Wild 2

Abstract— Among the samples returned from comet 81P/Wild 2 by the Stardust spacecraft is a suite of particles from one impact track (Track 25) that are Ca‐, Al‐rich and FeO‐free. We studied three particles from this track that range in size from 5.3 × 3.2 μ to 15 × 10 μ. Scanning and transmission electron microscopy show that they consist of very fine‐grained (typically from ?0.5 to ?2 μ) Al‐rich, Ti‐bearing and Ti‐free clinopyroxene, Mg‐Al spinel and anorthite, with trace amounts of fine perovskite, FeNi metal and osbornite (TiN) grains. In addition to these phases, the terminal particle, named “Inti”, also contains melilite. All of these phases, with the exception of osbornite, are common in refractory inclusions and are predicted to condense at high temperature from a gas of solar composition. Osbornite, though very rare, has also been found in meteoritic refractory inclusions, and could have formed in a region of the nebula where carbon became enriched relative to oxygen compared to solar composition. Compositions of Ti‐pyroxene in Inti are similar, but not identical, to those of fassaite from Allende inclusions. Electron energy loss spectroscopy shows that Ti‐rich pyroxene in Inti has Ti³⁺/Ti⁴⁺within the range of typical meteoritic fassaite, consistent with formation under reducing conditions comparable to those of a system of solar composition. Inti is ¹⁶O‐rich, with δ₁₈O?δ¹⁷O?‐40%0, like unaltered phases in refractory inclusions and refractory IDPs. With grain sizes, mineralogy, mineral chemistry, and an oxygen isotopic composition like those of refractory inclusions, we conclude that Inti is a refractory inclusion that formed in the inner solar nebula. Identification of a particle that formed in the inner solar system among the comet samples demonstrates that there was transport of materials from the inner to the outer nebula, probably either in a bipolar outflow or by turbulence.     

Photometric modeling of Asteroid 5535 Annefrank from Stardust observations

In this paper the Stardust disk-integrated phase curve at phase 47.2-134.6° of the Asteroid 5535 Annefrank, combined with groundbased observations (at phase 2.3-18.3°), are fit with Hapke’s photometric model. We confirm Newburn et al.’s (Newburn, R.L. et al. [2003]. J. Geophys. Res. 108 (E11), 5117. doi:10.1029/2003JE002106) observation that Annefrank exhibits a steep phase curve. This manifests itself in an unusually high fit surface roughness parameter of 49°. The single particle scattering albedo is 0.62, also high for an S-asteroid, while the fit phase function is more forward scattering than the typical S-asteroid being nearly isotropic with an asymmetry parameter of −0.09. The fit opposition surge width (h = 0.015) is typical of S-asteroids. However these fits assume a spherical shape to the asteroid. Li et al. (Li, J., A’Hearn, M.F., McFadden, L.A. [2004]. Icarus, 415-431) have shown that this assumption may lead to significant errors particularly at high phase angles leading to higher modeled single particle scattering albedos, macroscopic roughnesses and more forward scattering phase functions than actually exhibited. Our results confirm this finding—fitting only the data below 90° phase yields lower particle albedos (0.41) and roughnesses (20°) and more backscattering particles (−0.19) than the fit including the high phase angle data. Overall Annefrank appears to be on the bright side but otherwise is typical for an S-type asteroid suggesting that it may be a recent collisional fragment with a relatively immature surface which has had relatively little time to be weathered.     

A TEM and EELS study of carbon in a melt fragment from the Gardnos impact structure

A carbon‐rich melt fragment from the Gardnos impact structure has been studied for a better understanding of the preservation and structural form(s) of carbon that have been processed by impact melting. The carbon was analyzed in situ in its original petrographic context within the melt fragment, using high‐resolution techniques including focused ion beam‐transmission electron microscopy and electron energy loss spectroscopy. Results show that the carbon is largely uniform and has a nanocrystalline grain size. The Gardnos carbon has a graphitic structure but with a large c/a ratio indicating disorder. The disorder could be a result of rapid heating to high temperatures during impact, followed by rapid cooling, with not enough time to crystallize into highly ordered graphite. However, temperature distribution during impact is extremely heterogenous, and the disordered Gardnos carbon could also represent material that avoided extreme temperatures, and thus, it was preserved. Understanding the structure of carbon during terrestrial impacts is important to help determine if the history of carbon within extraterrestrial samples is impact related. Furthermore, the degree of preservation of carbon during impact is key for locating and detecting organic compounds in extraterrestrial samples. This example from Gardnos, together with previous studies, shows that not all carbon is lost to oxidation during impact but that impact melting can encapsulate and preserve carbon where it is available.     

Reanalysis of four NASA stratospheric particles

Four stratospheric contaminants catalogued in the Cosmic Dust Catalogs published by the NASA Johnson Space Center (JSC) in Houston were reanalysed. The results are compatible with those obtained in JSC, however additional features have occurred in our chemical analyses and their interpretation is also discussed.     

At the interface of silica glass and compressed silica aerogel in Stardust track 10: Comet Wild 2 is not a goldmine

In Stardust tracks C2044,0,38, C2044,0,39, and C2044,0,42 (Brennan et al. 2007 ) and Stardust track 10 (this work) gold is present in excess of its cosmochemical abundance. Ultra‐thin sections of allocation FC6,0,10,0,26 (track 10) show a somewhat wavy, compressed silica aerogel/silica glass interface which challenges exact location identification, i.e., silica glass, compressed silica aerogel, or areas of overlap. In addition to domains of pure silica ranging from SiO₂ to SiO₃ glass, there is MgO‐rich silica glass with a deep metastable composition, MgO = 14 ± 6 wt%, due to assimilation of Wild 2 Mg‐silicate matter in silica melt. This magnesiosilica composition formed when temperatures during hypervelocity capture reached >2000 °C followed by ultrafast quenching of the magnesiosilica melt when it came into contact with compressed aerogel at ~155 °C. The compressed silica aerogel in track 10 has a continuous Au background as result of the melting point depression of gold particles <5 nm that showed liquid‐like behavior. Larger gold particles are scattered found throughout the silica aerogel matrix and in aggregates up to ~50 nm in size. No gold is found in MgO‐rich silica glass. Gold in track 10 is present at the silica aerogel/silica glass interface. In the other tracks gold was likely near‐surface contamination possibly from an autoclave used in processing of these particular aerogel tiles. So far gold contamination is documented in these four different tracks. Whether they are the only tiles with gold present in excess of its cosmochemical abundance or whether more tiles will show excess gold abundances is unknown.     

The analysis of four cosmic dust particles

A set of four stratospheric particles was reanalysed. These particles registered in the NASA Cosmic Dust Catalogs (CDCs) were classified in the Houston Johnson Space Center (JSC) as the particles of cosmic origin (C). Present energy-dispersive X-ray (EDX) spectra confirmed previous classification and revealed additional features in the chemical composition of the cosmic dust particles.The particles are extremely fine-grained aggregates with bulk chondritic composition. Somewhat higher content of oxygen may indicate a presence of hydroxide containing minerals in their phase composition.     

Investigation of ion beam techniques for the analysis and exposure of particles encapsulated by silica aerogel: Applicability for Stardust

Abstract— In 2006, the Stardust spacecraft will return to Earth with cometary and perhaps interstellar dust particles embedded in silica aerogel collectors for analysis in terrestrial laboratories. These particles will be the first sample return from a solid planetary body since the Apollo missions. In preparation for the return, analogue particles were implanted into a keystone of silica aerogel that had been extracted from bulk silica aerogel using the optical technique described in Westphal et al. (2004). These particles were subsequently analyzed using analytical techniques associated with the use of a nuclear microprobe. The particles have been analyzed using: a) scanning transmission ion microscopy (STIM) that enables quantitative density imaging; b) proton elastic scattering analysis (PESA) and proton backscattering (PBS) for the detection of light elements including hydrogen; and c) proton‐induced X‐ray emission (PIXE) for elements with Z > 11. These analytical techniques have enabled us to quantify the composition of the encapsulated particles. A significant observation from the study is the variable column density of the silica aerogel. We also observed organic contamination within the silica aerogel. The implanted particles were then subjected to focused ion beam (FIB) milling using a 30 keV gallium ion beam to ablate silica aerogel in site‐specific areas to expose embedded particles. An ion polished flat surface of one of the particles was also prepared using the FIB. Here, we show that ion beam techniques have great potential in assisting with the analysis and exposure of Stardust particles.     

Surface modifications of comet‐exposed aerogel from the Stardust cometary collector

Abstract– Keystones removed from the Stardust cometary collector show varying degrees of visible fluorescence when exposed to UV light, with the brightest fluorescence associated with the space‐exposed surface. We investigated the spatial characteristics of this phenomenon further by using fluorescence microscopy, confocal Raman microscopy, and synchrotron Fourier transform infrared (FTIR) spectromicroscopy. Twenty‐four keystones, extracted from the Stardust cometary collector, were analyzed. Fluorescence measurements show two distributions with different excitation characteristics, indicating the presence of at least two distinct fluorophores. The first distribution is confined to within about 10 μm of the space‐exposed surface, whereas the second distribution is much broader with a maximum that is typically about 30–50 μm below the surface. Confocal Raman measurements did not reveal any changes associated with the surface; however, only features associated with aliphatic hydrocarbons were strong enough to be observed. FTIR measurements, on the other hand, show two distinct distributions at the space‐exposed surface: (1) a narrow, surface‐confined distribution originating from ?O₃SiH groups and (2) a broader, sub‐surface distribution originating from ?O₂SiH₂ groups. These functional groups were not observed in keystones extracted from the cometary flight spare or from the Stardust interstellar collector, indicating that they may result at least partially from cometary exposure. The presence of O₃SiH and O₂SiH₂ groups at the comet‐exposed surface suggests that the enhanced surface fluorescence is caused by defects in the O‐Si‐O network and not by organic contamination.     

Three‐dimensional shapes and Fe contents of Stardust impact tracks: A track formation model and estimation of comet Wild 2 coma dust particle densities

Abstract– We investigated three‐dimensional structures of comet Wild 2 coma particle impact tracks using synchrotron radiation (SR) X‐ray microtomography at SPring‐8 to elucidate the nature of comet Wild 2 coma dust particles captured in aerogel by understanding the capture process. All tracks have a similar entrance morphology, indicating a common track formation process near the entrance by impact shock propagation irrespective of impactor materials. Distributions of elements along the tracks were simultaneously measured using SR‐XRF. Iron is distributed throughout the tracks, but it tends to concentrate in the terminal grains and at the bottoms of bulbs. Based on these results, we propose an impact track formation process. We estimate the densities of cometary dust particles based on the hypothesis that the kinetic energy of impacting dust particles is proportional to the track volume. The density of 148 cometary dust particles we investigated ranges from 0.80 to 5.96 g cm^?3 with an average of 1.01 (±0.25) g cm^?3. Moreover, we suggest that less fragile crystalline particles account for approximately 5 vol% (20 wt%) of impacting particles. This value of crystalline particles corresponds to that of chondrules and CAIs, which were transported from the inner region of the solar system to the outer comet‐forming region. Our results also suggest the presence of volatile components, such as organic material and perhaps ice, in some bulbous tracks (type‐C).     

Photometric analysis of the nucleus of Comet 81P/Wild 2 from Stardust images

The disk-resolved flyby images of the nucleus of Comet 81P/Wild 2 collected by Stardust are used to perform a detailed study of the photometric properties of this cometary nucleus. A disk-integrated phase function from phase angle 11° to about 100° is measured and modeled. A phase slope of 0.0513 ± 0.0002 mag/deg is found, with a V-band absolute magnitude of 16.29 ± 0.02. Hapke’s photometric model yields a single-scattering albedo of 0.034, an asymmetry factor of phase function −0.53, a geometric albedo 0.059, and a V-band absolute magnitude of 16.03 ± 0.07. Disk-resolved photometric modeling from both the Hapke model and the Minnaert model results in 11% model RMS, indicating small photometric variations. The roughness parameter is modeled to be 27 ± 5° from limb-darkening profile. The modeled single-scattering albedo and asymmetry factor of the phase function are 0.038 ± 0.004 and −0.52 ± 0.04, respectively, consistent with those from disk-integrated phase function. The bulk photometric properties of the nucleus of Wild 2 are comparable with those of other cometary nuclei. The photometric variations on the surface of the nucleus of Wild 2 are at a level of or smaller than 15%, much smaller than those on the nucleus of Comet 19P/Borrelly and comparable or smaller than those on the nucleus of Comet 9P/Tempel 1. The similar photometric parameters of the nuclei of Wild 2, Tempel 1, and the non-source areas of fan jets on Borrelly may reflect the typical photometric properties of the weakly active surfaces on cometary nuclei.     

Understanding the mechanisms of formation of nanophase compounds from Stardust: Combined experimental and observational approach

Abstract– We have experimentally produced nanophase sulfide compounds and magnetite embedded in Si‐rich amorphous materials by flash‐cooling of a gas stream. Similar assemblages are ubiquitous, and often dominant components of samples of impact‐processed silica aerogel tiles and submicron grains from comet 81P/Wild 2 were retrieved by NASA’s Stardust mission. Although the texture and compositions of nanosulfide compounds have been reproduced experimentally, the mechanisms of formation of these minerals and their relationship with the surrounding amorphous materials have not been established. In this study, we present evidence that both of these materials may not only be produced through cooling of a superheated liquid but they may have also been formed simultaneously by flash‐cooling and subsequent deposition of a gas dominated by Fe‐S‐SiO‐O₂. In a dust generator at the Goddard Space Flight Center, samples are produced by direct gas‐phase condensation from gaseous precursors followed by deposition, which effectively isolates the effects of gas‐phase reactions from the effects of melting and condensation. High‐resolution transmission electron microscopy images and energy‐dispersive spectroscopy analysis show that these experiments replicate key features of materials from type B and type C Stardust tracks, including textures, distribution of inclusions, nanophase size, and compositional diversity. We argue that gas‐phase reactions may have played a significant role in the capture environment for nanophase materials. Our results are consistent with a potential progenitor assemblage of micron and submicron‐sized sulfides and submicron silica‐bearing phases, which are commonly observed in chondritic interplanetary dust particles and in the matrices of the most pristine chondritic meteorites.     

A TEM study of exsolution in Ca-rich pyroxenes from the Paris and Renazzo chondrites: Determination of type I chondrule cooling rates

We conducted a transmission electron microscope study of the exsolution microstructures of Ca-rich pyroxenes in type I chondrules from the Paris CM and Renazzo CR carbonaceous chondrites in order to provide better constraints on the cooling history of type I chondrules. Our study shows a high variability of composition in the augite grains at a submicrometer scale, reflecting nonequilibrium crystallization. The microstructure is closely related to the local composition and is thus variable inside augite grains. For compositions inside the pyroxene miscibility gap, with a wollastonite (Wo) content typically below 40 mole%, the augite grains contain abundant exsolution lamellae on (001). For grain areas with composition close to Wo₄₀, a modulated texture on (100) and (001) is the dominant microstructure, while areas with compositions higher than Wo₄₀ do not show any exsolution microstructure development. To estimate the cooling rate, we used the spacing of the exsolution lamellae on (001), for which the growth is diffusion controlled and thus sensitive to the cooling rate. Despite the relatively homogeneous microstructures of augite grains with Wo < 35 mole%, our study of four chondrules suggests a range of cooling rates from ~10 to ~1000 °C h⁻¹, within the temperature interval 1200–1350 °C. These cooling rates are comparable to those of type II chondrules, i.e., 1–1000 °C h⁻¹. We conclude that the formation of type I and II chondrules in the proto-solar nebula was the result of a common mechanism.     

Along‐track compositional and textural variation in extensively melted grains returned from comet 81P/Wild 2 by the Stardust mission: Implications for capture‐melting process

Abstract— Five amorphous (extensively melted) grains from Stardust aerogel capture Track 35 were examined by transmission electron microscopy (TEM); two from the bulb, two from near the bulb‐stylus transition, and one from near the terminal particle. Melted grains consist largely of a texturally and compositionally heterogeneous emulsion of immiscible metal/sulfide beads nanometers to tens of nanometers in diameter in a silica‐rich vesicular glass. Most metal/sulfide beads are spherical, but textures of non‐spherical beads indicate that some solidified as large drops during stretching and breaking while in translational and rotational motion, and others solidified from lenses of immiscible liquid at the silicate‐melt/vesicle (vapor) interface. Melted grains appear to become richer in Fe relative to Mg, and depleted in S relative to Fe and Ni with increasing penetration distance along the aerogel capture track. Fe/S ratios are near unity in grains from the bulb of Track 35, consistent with the dominance of Fe‐monosulfide minerals inferred by previous research on Stardust materials. Near‐stoichiometric Fe/S in melted grains from the bulb suggests that Fe‐sulfides in the bulb were dispersed and melted during formation of the bulb but did not lose S. Along‐track increases in Fe/S in melted grains from the bulb through the bulb‐stylus transition and continuing into the stylus indicate that S initially present as iron monosulfide may have been progressively partially volatilized and lost from the melted grains with greater penetration of the grains deeper into the aerogel during capture‐melting of comet dust. Extensively melted grains from the bulbs of aerogel capture tracks may preserve better primary compositional information with less capture‐related modification than grains from farther along the same capture tracks.     

Microstructural study of micron‐sized craters simulating Stardust impacts in aluminum 1100 targets

Abstract— Various microscopic techniques were used to characterize experimental microcraters in aluminum foils to prepare for the comprehensive analysis of the cometary and interstellar particle impacts in aluminum foils to be returned by the Stardust mission. First, scanning electron microscopy (SEM) and energy dispersive X‐ray spectroscopy (EDS) were used to study the morphology of the impact craters and the bulk composition of the residues left by soda‐lime glass impactors. A more detailed structural and compositional study of impactor remnants was then performed using transmission electron microscopy (TEM), EDS, and electron diffraction methods. The TEM samples were prepared by focused ion beam (FIB) methods. This technique proved to be especially valuable in studying impact crater residues and impact crater morphology. Finally, we also showed that infrared microscopy (IR) can be a quick and reliable tool for such investigations. The combination of all of these tools enables a complete microscopic characterization of the craters.     

Helium and neon in comet 81P/Wild 2 samples from the NASA Stardust mission

Helium and neon distributions are reported for a variety of Stardust comet 81P/Wild 2 samples, including particle tracks and terminal particles, cell surface and subsurface slices from the comet coma and interstellar particle collection trays, and numerous small aerogel blocks extracted from comet cells C2044 and C2086. Discussions and conclusions in several abstracts published during the course of the investigation are included, along with the relevant data. Measured isotope ratios span a broad range, implying a similar range for noble gas carriers in the Wild 2 coma. The meteoritic phase Q‐²⁰Ne/²²Ne ratio was observed in several samples. Some of these, and others, exhibit ²¹Ne excesses too large for attribution to spallation by galactic cosmic ray irradiation, suggesting exposure to a solar proton flux greatly enhanced above current levels in an early near‐Sun environment. Still others display evidence for a solar wind component, particularly one C2086 block with large abundances of isotopically solar‐like helium and neon. Eighty‐nine small aerogel samples were cut from depths up to several millimeters below the cell C2044 surface and several millimeters away from the axis of major track T41. A fraction of these yielded measurable and variable helium and neon abundances and isotope ratios, although none contained visible tracks or carrier particle fragments and their locations were beyond estimated penetration ranges for small particles or ions incident on the cell surface, or for lateral ejecta from T41. Finding plausible emplacement mechanisms and sources for these gases is a significant challenge raised by this study.