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.     

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.     

Three‐dimensional textural and compositional analysis of particle tracks and fragmentation history in aerogel

Abstract— We report analyses of aerogel tracks using (1) synchrotron X‐ray computed microtomography (XRCMT), (2) laser confocal scanning microscopy (LCSM), and (3) synchrotron radiation X‐ray fluorescence (SRXRF) of particles and their paths resulting from simulated hypervelocity impacts (1–2), and a single ～1 mm aerogel track from the Stardust cometary sample collector (1–3). Large aerogel pieces can be imaged sequentially, resulting in high spatial resolution images spanning many tomographic fields of view (‘lambda‐tomography’). We report calculations of energy deposited, and tests on aromatic hydrocarbons showing no alteration in tomography experiments. Imaging at resolutions from ～17 to ～1 micron/pixel edge (XRCMT) and to <100 nm/pixel edge (LCSM) illustrates track geometry and interaction of particles with aerogel, including rifling, particle fragmentation, and final particle location. We present a 3‐D deconvolution method using an estimated point‐spread function for aerogel, allowing basic corrections of LCSM data for axial distortion. LCSM allows rapid, comprehensive, non‐destructive, high information return analysis of tracks in aerogel keystones, prior to destructive grain extraction. SRXRF with LCSM allows spatial correlation of grain size, chemical, and mineralogical data. If optical methods are precluded in future aerogel capture missions, XRCMT is a viable 3D imaging technique. Combinations of these methods allow for complete, nondestructive, quantitative 3‐D analysis of captured materials at high spatial resolution. This data is fundamental to understanding the hypervelocity particle‐aerogel interaction histories of Stardust grains.     

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.     

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).     

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.     

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.     

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).     

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.     

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.     

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.     

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.     

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).     

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.     

Small hypervelocity particles captured in aerogel collectors: Location,extraction, handling and storage

Abstract— It has now been about a decade since the first demonstrations that hypervelocity particles could be captured, partially intact, in aerogel collectors. But the initial promise of a bonanza of partially‐intact extraterrestrial particles, collected in space, has yet to materialize. One of the difficulties that investigators have encountered is that the location, extraction, handling and analysis of very small (10 μm and less) grains, which constitute the vast majority of the captured particles, is challenging and burdensome. Furthermore, current extraction techniques tend to be destructive over large areas of the collectors. Here we describe our efforts to alleviate some of these difficulties. We have learned how to rapidly and efficiently locate captured particles in aerogel collectors, using an automated microscopic scanning system originally developed for experimental nuclear astrophysics. We have learned how to precisely excavate small access tunnels and trenches using an automated micromanipulator and glass microneedles as tools. These excavations are only destructive to the collector in a very small area—this feature may be particularly important for excavations in the precious Stardust collectors. Using actuatable silicon microtweezers, we have learned how to extract and store “naked” particles—essentially free of aerogel—as small as 3 μm in size. We have also developed a technique for extracting particles, along with their terminal tracks, still embedded in small cubical aerogel blocks. We have developed a novel method for storing very small particles in etched nuclear tracks. We have applied these techniques to the extraction and storage of grains captured in aerogel collectors (Particle Impact Experiment, Orbital Debris Collector Experiment, Comet‐99) in low Earth orbit.     

Correlated microanalysis of cometary organic grains returned by Stardust

Abstract– Carbonaceous matter in Stardust samples returned from comet 81P/Wild 2 is observed to contain a wide variety of organic functional chemistry. However, some of this chemical variety may be due to contamination or alteration during particle capture in aerogel. We investigated six carbonaceous Stardust samples that had been previously analyzed and six new samples from Stardust Track 80 using correlated transmission electron microscopy (TEM), X‐ray absorption near‐edge structure spectroscopy (XANES), and secondary ion mass spectroscopy (SIMS). TEM revealed that samples from Track 35 containing abundant aliphatic XANES signatures were predominantly composed of cometary organic matter infilling densified silica aerogel. Aliphatic organic matter from Track 16 was also observed to be soluble in the epoxy embedding medium. The nitrogen‐rich samples in this study (from Track 22 and Track 80) both contained metal oxide nanoparticles, and are likely contaminants. Only two types of cometary organic matter appear to be relatively unaltered during particle capture. These are (1) polyaromatic carbonyl‐containing organic matter, similar to that observed in insoluble organic matter (IOM) from primitive meteorites, interplanetary dust particles (IDPs), and in other carbonaceous Stardust samples, and (2) highly aromatic refractory organic matter, which primarily constitutes nanoglobule‐like features. Anomalous isotopic compositions in some of these samples also confirm their cometary heritage. There also appears to be a significant labile aliphatic component of Wild 2 organic matter, but this material could not be clearly distinguished from carbonaceous contaminants known to be present in the Stardust aerogel collector.     

Macroscopic subdivision of silica aerogel collectors for sample return missions

Abstract— Silica aerogel collector tiles have been employed for the collection of particles in low Earth orbit and, more recently, for the capture of cometary particles by NASA's Stardust mission. Reliable, reproducible methods for cutting these and future collector tiles from sample return missions are necessary to maximize the science output from the extremely valuable embedded particles. We present a means of macroscopic subdivision of collector tiles by generating large‐scale cuts over several centimeters in silica aerogel with almost no material loss. The cut surfaces are smooth and optically clear allowing visual location of particles for analysis and extraction. This capability is complementary to the smaller‐scale cutting capabilities previously described (Westphal 2004; Ishii 2005a, 2005b) for removing individual impacts and particulate debris in tiny aerogel extractions. Macroscopic cuts enable division and storage or distribution of portions of aerogel tiles for immediate analysis of samples by certain techniques in situ or further extraction of samples suited for other methods of analysis. The capability has been implemented in the Stardust Laboratory at NASA's Johnson Space Center as one of a suite of aerogel cutting methods to be used in Stardust sample curation.     

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.     

Raman spectroscopic investigation of two grains from comet 81P/Wild 2: Information that can be obtained beyond the presence of sp2‐bonded carbon

Abstract– Raman analyses were performed of individual micrometer‐sized fragments of material returned to Earth by the NASA Stardust mission to comet 81P/Wild 2. The studied fragments originated from grains (C2054,0,35,91,0 and C2092,6,80,51,0) of two different penetration tracks that occurred in two different silica aerogel collector cells. All fragments of both particles have Raman spectra characteristic of amorphous sp²‐bonded carbon that are in general agreement with the results published in previous Stardust particle studies. The present study, however, does not focus on the discussion of specific details of the D and G band parameters, but rather reports on additional information that can be obtained from returned Stardust samples via Raman spectroscopy. Most notably, the Raman spectra show that all analyzed fragments of the particles were contaminated with the capture medium (i.e., aerogel). The silica aerogel is laced with organic aliphatic and aromatic hydrocarbon impurities that resulted in strong bands in the ～ 2900 Δcm^?1 spectral range (C‐H stretching modes). Aerogel bands are also found in the 1000–1600 Δcm^?1 spectral range, where they overlap with the bands of the amorphous sp²‐bonded carbon. The peaks associated with the aerogel contamination differ between the two grains that originated from two different aerogel cells. In addition to the bands due to aerogel contamination and the always present sp²‐bonded carbon bands, fragments of particle C2092,6,80,51,0 also show Raman peaks for pyrrhotite and Fa₃₀Fo₇₀ olivine. Complete (up to 4000 Δcm^?1) raw and baseline‐corrected Raman spectra of the Stardust particles are shown and discussed in detail.