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).     

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.     

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.     

Experimental impact features in Stardust aerogel: How track morphology reflects particle structure,composition, and density

Abstract– The Stardust collector shows diverse aerogel track shapes created by impacts of cometary dust. Tracks have been classified into three broad types (A, B, and C), based on relative dimensions of the elongate “stylus” (in Type A “carrots”) and broad “bulb” regions (Types B and C), with occurrence of smaller “styli” in Type B. From our experiments, using a diverse suite of projectile particles shot under Stardust cometary encounter conditions onto similar aerogel targets, we describe differences in impactor behavior and aerogel response resulting in the observed range of Stardust track shapes. We compare tracks made by mineral grains, natural and artificial aggregates of differing subgrain sizes, and diverse organic materials. Impacts of glasses and robust mineral grains generate elongate, narrow Type A tracks (as expected), but with differing levels of abrasion and lateral branch creation. Aggregate particles, both natural and artificial, of a wide range of compositions and volatile contents produce diverse Type B or C shapes. Creation of bulbous tracks is dependent upon impactor internal structure, grain size distribution, and strength, rather than overall grain density or content of volatile components. Nevertheless, pure organic particles do create Type C, or squat Type A* tracks, with length to width ratios dependent upon both specific organic composition and impactor grain size. From comparison with the published shape data for Stardust aerogel tracks, we conclude that the abundant larger Type B tracks on the Stardust collector represent impacts by particles similar to our carbonaceous chondrite meteorite powders.     

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.     

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.     

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.     

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).     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.