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).     

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).     

Rapid extraction of dust impact tracks from silica aerogel by ultrasonic microblades

Abstract— In January 2006, NASA's Stardust mission will return with its valuable cargo of the first cometary dust particles captured at hypervelocity speeds in silica aerogel collectors and brought back to Earth. Aerogel, a proven capture medium, is also a candidate for future sample return missions and low‐Earth orbit (LEO) deployments. Critical to the science return of Stardust as well as future missions that will use aerogel is the ability to efficiently extract impacted particles from collector tiles. Researchers will be eager to obtain Stardust samples as quickly as possible; tools for the rapid extraction of particle impact tracks that require little construction, training, or investment would be an attractive asset. To this end, we have experimented with diamond and steel microblades. Applying ultrasonic frequency oscillations to these microblades via a piezo‐driven holder produces rapid, clean cuts in the aerogel with minimal damage to the surrounding collector tile. With this approach, intact impact tracks and associated particles in aerogel fragments with low‐roughness cut surfaces have been extracted from aerogel tiles flown on NASA's Orbital Debris Collector (ODC) experiment. The smooth surfaces produced during cutting reduce imaging artifacts during analysis by scanning electron microscopy (SEM). Some tracks have been dissected to expose the main cavity for eventual isolation of individual impact debris particles and further analysis using techniques such as transmission electron microscopy (TEM) and nano‐secondary ion mass spectrometry (nanoSIMS).     

Fine‐grained material of 81P/Wild 2 in interaction with the Stardust aerogel

Abstract– The deceleration tracks in the Stardust aerogel display a wide range of morphologies, which reveal a large diversity of incoming particles from comet 81P/Wild 2. If the large and dense mineral grains survived the extreme conditions of hypervelocity capture, this was not the case for the fine‐grained material that is found strongly damaged within the aerogel. Due to their low mechanical strength, these assemblages were disaggregated, dispersed, and flash melted in the aerogel in walls of bulbous deceleration tracks. Their petrologic and mineralogical properties are found significantly modified by the flash heating of the capture. Originating from a quenched melt mixture of comet material and aerogel, the representative microstructure consists of silica‐rich glassy clumps containing Fe‐Ni‐S inclusions, vesicles and “dust‐rich” patches, the latter being remnants of individual silicate components of the impacting aggregate. The average composition of these melted particle fragments is close to the chondritic CI composition. They might originate from ultrafine‐grained primitive components comparable to those found in chondritic porous IDPs. Capture effects in aerogel and associated sample biases are discussed in terms of size, chemical and mineralogical properties of the grains. These properties are essential for the grain survival in the extremely hot environment of hypervelocity impact capture in aerogel, and thus for inferring the correct properties of Wild 2 material.     

Hypervelocity capture of meteoritic particles in nonsilica aerogels

Abstract– The Stardust mission captured particles from the comet 81P/Wild 2 in gradient density silica aerogel and returned the collected samples to earth in 2006. The analyses of these particles have revealed several new insights into the formation of our solar system. However, since the aerogel used as the capture material was silica, the elemental analyses of the silica‐rich particles were made more complicated in certain ways due to the mixing of the silicon of the particles and that of the aerogel. By using a nonsilica aerogel, future elemental analyses of silica–rich particles captured in aerogel could be made more straightforward. Resorcinol/formaldehyde (RF), alumina, and zirconia aerogels were impact tested with meteoritic fragments and the captured fragments were mapped with synchrotron‐based X‐ray microprobe (XRM) and the particles were analyzed with X‐ray fluorescence (XRF). The resorcinol/formaldehyde aerogel proved to be the best capture material, in that it could be keystoned and XRF could be used to locate and analyze particles that were less than 10 μm.     

Time evolution and temperatures of hypervelocity impact‐generated tracks in aerogel

Abstract— Aerogel collectors have been used to capture cometary, interplanetary, and interstellar dust grains by NASA's Stardust mission, highlighting their importance as a scientific instrument. Due to the fragile and heterogeneous nature of cometary dust grains, their fragments are found along the walls of tracks that are formed during the capture process. These fragments appear to experience a wide range of thermal alteration and the causes of this variation are not well understood at a theoretical level as physical models of track formation are not well developed. Here, a general model of track formation that allows for the existence of partially and completely vaporized aerogel material in tracks is developed. It is shown that under certain conditions, this general track model reduces to the kinetic “snowplow” model that has previously been proposed. It is also shown, based on energetic considerations, that track formation is dominated by an expansion that is snowplow‐like in the later stages of track formation. The equation of motion for this snowplow‐like stage can be solved analytically, thus placing constraints on the amount of heating experienced by cometary dust fragments embedded in track walls. It is found that the heating of these fragments, for a given impact velocity, is expected to be greater for those embedded in larger tracks. Given the expected future use of aerogels for sample return missions, the results presented here imply that the choice of aerogel compositions can have a significant effect on the modification of samples captured and retrieved by these collectors.     

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.     

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.     

Complex aromatic hydrocarbons in Stardust samples collected from comet 81P/Wild 2

Abstract– The successful return of the Stardust spacecraft provides a unique opportunity to investigate the nature and distribution of organic matter in cometary dust particles collected from comet 81P/Wild 2. Analysis of individual cometary impact tracks in silica aerogel using the technique of two‐step laser mass spectrometry demonstrates the presence of complex aromatic organic matter. While concerns remain as to the organic purity of the aerogel collection medium and the thermal effects associated with hypervelocity capture, the majority of the observed organic species appear indigenous to the impacting particles and are hence of cometary origin. While the aromatic fraction of the total organic matter present is believed to be small, it is notable in that it appears to be N rich. Spectral analysis in combination with instrumental detection sensitivies suggest that N is incorporated predominantly in the form of aromatic nitriles (R–C≡N). While organic species in the Stardust samples do share some similarities with those present in the matrices of carbonaceous chondrites, the closest match is found with stratospherically collected interplanetary dust particles. These findings are consistent with the notion that a fraction of interplanetary dust is of cometary origin. The presence of complex organic N containing species in comets has astrobiological implications as comets are likely to have contributed to the prebiotic chemical inventory of both the Earth and Mars.     

Non‐silica aerogels as hypervelocity particle capture materials

Abstract– The Stardust sample return mission to the comet Wild 2 used silica aerogel as the principal cometary and interstellar particle capture and return medium. However, since both cometary dust and interstellar grains are composed largely of silica, using a silica collector complicates the science that can be accomplished with these particles. The use of non‐silica aerogel in future extra‐terrestrial particle capture and return missions would expand the scientific value of these missions. Alumina, titania, germania, zirconia, tin oxide, and resorcinol/formaldehyde aerogels were produced and impact tested with 20, 50, and 100 μm glass microspheres to determine the suitability of different non‐silica aerogels as hypervelocity particle capture mediums. It was found that non‐silica aerogels do perform as efficient hypervelocity capture mediums, with alumina, zirconia, and resorcinol/formaldehyde aerogels proving to be the best of the materials tested.     

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.     

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.     

Properties of original impactors estimated from three‐dimensional analysis of whole Stardust tracks

Abstract– The Stardust mission captured comet Wild 2 particles in aerogel at 6.1 km s^?1. We performed high‐resolution three‐dimensional imaging and X‐ray fluorescence mapping of whole cometary tracks in aerogel. We present the results of a survey of track structures using laser scanning confocal microscopy, including measurements of track volumes, entry hole size, and cross‐sectional profiles. We compare various methods for measuring track parameters. We demonstrate a methodology for discerning hypervelocity particle ablation rates using synchrotron‐based X‐ray fluorescence, combined with mass and volume estimates of original impactors derived from measured track properties. Finally, we present a rough framework for reconstruction of original impactor size, and volume of volatilized material, using our measured parameters. The bulk of this work is in direct support of nondestructive analysis and identification of cometary grains in whole tracks, and its eventual application to the reconstruction of the size, shape, porosity, and chemical composition of whole Stardust impactors.     

Focused ion beam recovery of hypervelocity impact residue in experimental craters on metallic foils

Abstract— The Stardust sample return capsule returned to Earth in January 2006 with primitive debris collected from comet 81P/Wild‐2 during the flyby encounter in 2004. In addition to the cometary particles embedded in low‐density silica aerogel, there are microcraters preserved in the aluminum foils (1100 series; 100 μm thick) that are wrapped around the sample tray assembly. Soda lime spheres (?49 μm in diameter) have been accelerated with a light gas gun into flight‐grade aluminum foils at 6.35 km s^?1 to simulate the capture of cometary debris. The experimental craters have been analyzed using scanning electron microscopy (SEM) and X‐ray energy dispersive spectroscopy (EDX) to locate and characterize remants of the projectile material remaining within the craters. In addition, ion beam‐induced secondary electron imaging has proven particularly useful in identifying areas within the craters that contain residue material. Finally, high‐precision focused ion beam (FIB) milling has been used to isolate and then extract an individual melt residue droplet from the interior wall of an impact. This has enabled further detailed elemental characterization that is free from the background contamination of the aluminum foil substrate. The ability to recover “pure” melt residues using FIB will significantly extend the interpretations of the residue chemistry preserved in the aluminum foils returned by Stardust.     

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.     

Nanometer‐scale anatomy of entire Stardust tracks

Abstract– We have developed new sample preparation and analytical techniques tailored for entire aerogel tracks of Wild 2 sample analyses both on “carrot” and “bulbous” tracks. We have successfully ultramicrotomed an entire track along its axis while preserving its original shape. This innovation allowed us to examine the distribution of fragments along the entire track from the entrance hole all the way to the terminal particle. The crystalline silicates we measured have Mg‐rich compositions and O isotopic compositions in the range of meteoritic materials, implying that they originated in the inner solar system. The terminal particle of the carrot track is a ¹⁶O‐rich forsteritic grain that may have formed in a similar environment as Ca‐, Al‐rich inclusions and amoeboid olivine aggregates in primitive carbonaceous chondrites. The track also contains submicron‐sized diamond grains likely formed in the solar system. Complex aromatic hydrocarbons distributed along aerogel tracks and in terminal particles. These organics are likely cometary but affected by shock heating.     

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.     

TOF‐SIMS analysis of Allende projectiles shot into silica aerogel

Abstract— Powdered Allende projectiles were fired into silica aerogel at 6.1 km/sec in order to evaluate particle retrieval and analysis techniques for samples from the Stardust mission. Since particles may disintegrate and ablate along the penetration paths in a high‐porosity aerogel, TOF‐SIMS analysis may be a suitable method to determine the distribution of such materials along the tracks as well as potential compositional modifications. Therefore, two ?350 μm‐sized tracks, residing at the surface of a keystone specimen that was flattened between two silicon chips, were analyzed. TOF‐SIMS allows for a detailed study of the chemical composition of particles that survived the impact mostly intact and of fine‐grained material from disintegrated projectiles. In the investigated keystone, material from light gas gun debris dominated. Besides the two tracks, a continuous, 40‐μm‐thick surface layer of implanted material—probably gun residue—was found. One of the two analyzed tracks is compositionally distinct from this surface layer and is likely to contain residual material of an Allende projectile. The analyses clearly demonstrate that tracks, resulting from impactors in the 5–10 μm size range, can be successfully analyzed with TOF‐SIMS.     

Three‐dimensional structures and elemental distributions of Stardust impact tracks using synchrotron microtomography and X‐ray fluorescence analysis

Abstract— Three‐dimensional structures and elemental abundances of four impact tracks in silica aerogel keystones of Stardust samples from comet 81P/Wild 2 (bulbous track 67 and carrot‐type tracks 46, 47, and 68) were examined non‐destructively by synchrotron radiation‐based microtomography and X‐ray fluorescence analysis. Track features, such as lengths, volumes and width as a function of track depth, were obtained quantitatively by tomography. A bulbous portion was present near the track entrance even in carrot‐type tracks. Each impact of a cometary dust particle results in the particle disaggregated into small pieces that were widely distributed on the track walls as well as at its terminal. Fe, S, Ca, Ni, and eight minor elements are concentrated in the bulbous portion of track 68 as well as in terminal grains. It was confirmed that bulbous portions and thin tracks were formed by disaggregation of very fine fragile materials and relatively coarse crystalline particles, respectively. The almost constant ratio of whole Fe mass to track volume indicates that the track volume is almost proportional to the impact kinetic energy. The size of the original impactor was estimated from the absolute Fe mass by assuming its Fe content (CI) and bulk density. Relations between the track sizes normalized by the impactor size and impact conditions are roughly consistent with those of previous hypervelocity impact experiments.     

Preparation of large Stardust aluminum foil craters for analysis

Over the last decade, silica aerogel tracks and aluminum foil craters on the Stardust collector have been studied extensively to determine the nature of captured cometary dust grains. Analysis of particles captured in aerogel has been developed to a fine art, aided by sophisticated preparation techniques, and yielding revolutionary knowledge of comet dust mineralogy. The Stardust foil craters can be interpreted in terms of impacting particle size and structure, but almost all studies of composition for their contents have relied on in situ analysis techniques or relatively destructive extraction of materials. This has limited their examination and interpretation. However, numerous experimental hypervelocity impact studies under Stardust-Wild 2 encounter conditions have shown that abundant dust components are preserved in foil craters of all sizes. Using some of these analogue materials, we have previously shown that modern, nondestructive scanning electron microscope imaging and X-ray microanalysis techniques can document distribution of dust remnants both quickly and thoroughly within foil craters prior to any preparation. Here we present findings from our efforts to quantify the amount of residue and demonstrate a simple method of crater shape modification which can bring material into positions where it is much more accessible for in situ analysis, or safe removal of small subsamples. We report that approximately 50% of silicate-dominated impactors were retained as impact crater residue; however, <3% of organic impactors remained in the craters after impact.