Organic matter from comet 81P/Wild 2, IDPs,and carbonaceous meteorites; similarities and differences

Abstract— During preliminary examination of 81P/Wild 2 particles collected by the NASA Stardust spacecraft, we analyzed seven, sulfur embedded and ultramicrotomed particles extracted from five different tracks. Sections were analyzed using a scanning transmission X‐ray microscope (SXTM) and carbon X‐ray absorption near edge structure (XANES) spectra were collected. We compared the carbon XANES spectra of these Wild 2 samples with a database of spectra on thirty‐four interplanetary dust particles (IDPs) and with several meteorites. Two of the particles analyzed are iron sulfides and there is evidence that an aliphatic compound associated with these particles can survive high temperatures. An iron sulfide from an IDP demonstrates the same phenomenon. Another, mostly carbon free containing particle radiation damaged, something we have not observed in any IDPs we have analyzed or any indigenous organic matter from the carbonaceous meteorites, Tagish Lake, Orgueil, Bells and Murchison. The carbonaceous material associated with this particle showed no mass loss during the initial analysis but chemically changed over a period of two months. The carbon XANES spectra of the other four particles varied more than spectra from IDPs and indigenous organic matter from meteorites. Comparison of the carbon XANES spectra from these particles with 1. the carbon XANES spectra from thirty‐four IDPs (<15 micron in size) and 2. the carbon XANES spectra from carbonaceous material from the Tagish Lake, Orgueil, Bells, and Murchison meteorites show that 81P/Wild 2 carbon XANES spectra are more similar to IDP carbon XANES spectra then to the carbon XANES spectra of meteorites.     

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.     

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.     

Laboratory simulation of impacts on aluminum foils of the Stardust spacecraft: Calibration of dust particle size from comet Wild‐2

Abstract— Metallic aluminum alloy foils exposed on the forward, comet‐facing surface of the aerogel tray on the Stardust spacecraft are likely to have been impacted by the same cometary particle population as the dedicated impact sensors and the aerogel collector. The ability of soft aluminum alloy to record hypervelocity impacts as bowl‐shaped craters offers an opportunistic substrate for recognition of impacts by particles of a potentially wide size range. In contrast to impact surveys conducted on samples from low Earth orbit, the simple encounter geometry for Stardust and Wild‐2, with a known and constant spacecraft‐particle relative velocity and effective surface‐perpendicular impact trajectories, permits closely comparable simulation in laboratory experiments. For a detailed calibration program, we have selected a suite of spherical glass projectiles of uniform density and hardness characteristics, with well‐documented particle size range from 10 μm to nearly 100 μm. Light gas gun buckshot firings of these particles at approximately 6 km s^?1 onto samples of the same foil as employed on Stardust have yielded large numbers of craters. Scanning electron microscopy of both projectiles and impact features has allowed construction of a calibration plot, showing a linear relationship between impacting particle size and impact crater diameter. The close match between our experimental conditions and the Stardust mission encounter parameters should provide another opportunity to measure particle size distributions and fluxes close to the nucleus of Wild‐2, independent of the active impact detector instruments aboard the Stardust spacecraft.     

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

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

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.     

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.     

A TEM study of four particles extracted from the Stardust track 80

Abstract— Four particles extracted from track 80 at different penetration depths have been studied by analytical transmission electron microscopy (ATEM). Regardless of their positions within the track, the samples present a comparable microstructure made of a silica rich glassy matrix embedding a large number of small Fe‐Ni‐S inclusions and vesicles. This microstructure is typical of strongly thermally modified particles that were heated and melted during the hypervelocity impact into the aerogel. X‐ray intensity maps show that the particles were made of Mg‐rich silicates (typically 200 nm in diameter) cemented by a fine‐grained matrix enriched in iron sulfide. Bulk compositions of the four particles suggest that the captured dust particle was an aggregate of grains with various iron sulfide fraction and that no extending chemical mixing in the bulb occurred during the deceleration. The bulk S/Fe ratios of the four samples are close to CI and far from the chondritic meteorites from the asteroidal belt, suggesting that the studied particles are compatible with chondritic‐porous interplanetary dust particles or with material coming from a large heliocentric distance for escaping the S depletion.     

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.     

Sulfur four isotope NanoSIMS analysis of comet‐81P/Wild 2 dust in impact craters on aluminum foil C2037N from NASA’s Stardust mission

Abstract– We present NanoSIMS four‐isotope S analyses of 24 comet Wild 2 dust impact residues in craters on aluminum foil C2037N returned by NASA’s Stardust mission. Except for one sample, all impact residues have normal S isotopic compositions within 2σ uncertainties of at least two S isotope ratios. This implies that most S‐rich Wild 2 dust impactors formed in the solar system. Instrumental isotope fractionation due to sample topography is the main contribution to our analytical uncertainty. One impact crater residue shows small anomalies of δ³³S = ?57 ± 17‰, and δ³⁴S = ?41 ± 17‰ (1σ uncertainties). Although this could be simply a statistical outlier or the fingerprint of a chemical isotope fractionation it is also possible that the observed anomaly results from the mixture of a cometary FeS particle with a small (150 nm diam.) presolar FeS supernova grain. This would translate into a presolar sulfide abundance of approximately 200 ppm.     

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).     

Two refractory Wild 2 terminal particles from a carrot‐shaped track characterized combining MIR/FIR/Raman microspectroscopy and FE‐SEM/EDS analyses

We present the analyses results of two bulk Terminal Particles, C2112,7,171,0,0 and C2112,9,171,0,0, derived from the Jupiter‐family comet 81P/Wild 2 returned by the Stardust mission. Each particle embedded in a slab of silica aerogel was pressed in a diamond cell. This preparation, as expected, made it difficult to identify the minerals and organic materials present in these particles. This problem was overcome using a combination of three different analytical techniques, viz. FE‐SEM/EDS, IR, and Raman microspectroscopy that allowed identifying the minerals and small amounts of amorphous carbon present in both particles. TP2 and TP3 were dominated by Ca‐free and low‐Ca, Mg‐rich, Mg,Fe‐olivine. The presence of melilite in both particles is supported by IR microspectroscopy, but is not confirmed by Raman microspectroscopy, possibly because the amounts are too small to be detected. TP2 and TP3 show similar silicate mineral compositions, but Ni‐free and low‐Ni, subsulfur (Fe,Ni)S grains are present in TP2 only. TP2 contains indigenous amorphous carbon hot spots; no indigenous carbon was identified in TP3. These nonchondritic particles probably originated in a differentiated body. This work found an unanticipated carbon contamination following the FE‐SEM/EDS analyses. It is suggested that organic materials in the embedding silica aerogel are irradiated during FE‐SEM/EDS analyses creating a carbon gas that develops a strong fluorescence continuum. The combination of the selected analytical techniques can be used to characterize bulk Wild 2 particles without the need of extraction and removal of the encapsulating aerogel. This approach offers a relatively fast sample preparation procedure, but compressing the samples can cause spurious artifacts, viz. silica contamination. Because of the combination of techniques, we account for these artifacts.     

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.     

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.     

Coordinated mineralogical and isotopic analyses of a cosmic symplectite discovered in a comet 81P/Wild 2 sample

We have discovered in a Stardust mission terminal particle a unique mineralogical assemblage of symplectically intergrown pentlandite ((Fe,Ni)₉S₈) and nanocrystalline maghemite (γ‐Fe₂O₃). Mineralogically similar cosmic symplectites (COS) have only been found in the primitive carbonaceous chondrite Acfer 094 and are believed to have formed by aqueous alteration. The O and S isotopic compositions of the Wild 2 COS are indistinguishable from terrestrial values. The metal and sulfide precursors were thus oxidized by an isotopically equilibrated aqueous reservoir either inside the snow line, in the Wild 2 comet, or in a larger Kuiper Belt object. Close association of the Stardust COS with a Kool mineral assemblage (kosmochloric Ca‐rich pyroxene, FeO‐rich olivine, and albite) that likely originated in the solar nebula suggests the COS precursors also had a nebular origin and were transported from the inner solar system to the comet‐forming region after they were altered.     

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

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

Comprehensive examination of large mineral and rock fragments in Stardust tracks: Mineralogy,analogous extraterrestrial materials,and source regions

Abstract– Transmission electron microscopy examination of 87 large fragments from 16 carrot‐shaped and bulbous Stardust (SD) tracks was performed to study the range and diversity of materials present in comet Wild 2. Olivines and low‐Ca pyroxenes represent the largest proportions of fragments observed; however, a wide range of minerals and rocks were found including probable ferromagnesian, Al‐rich and Si‐rich chondrule fragments, a refractory inclusion, possible matrix mineral/lithic clasts, and probable condensate minerals. These materials, combined with fine‐grained components in the tracks, are analogous to components in unequilibrated chondrite meteorites and cluster interplanetary dust particles (IDPs). Two unusual lithologies in the bulbous tracks are only observed in chondritic porous IDPs and may have direct links to IDPs. The absence of phyllosilicates indicates that comet Wild 2 may be a “dry” comet that did not accrete or form significant amounts of hydrated phases. Some large mineral fragments in the SD tracks are analogous to large mineral IDPs. The large variations of the coarse‐grained components within and between all 16 tracks show that comet Wild 2 is mineralogically diverse and unequilibrated on nearly all scales and must have accreted materials from diverse source regions that were widely dispersed throughout the solar nebula.     

Iron oxides in comet 81P/Wild 2

Abstract– We have used synchrotron Fe‐XANES, XRS, microRaman, and SEM‐TEM analyses of Stardust track 41 slice and track 121 terminal area slices to identify Fe oxide (magnetite‐hematite and amorphous oxide), Fe‐Ti oxide, and V‐rich chromite (Fe‐Cr‐V‐Ti‐Mn oxide) grains ranging in size from 200 nm to ～10 μm. They co‐exist with relict FeNi metal. Both Fe‐XANES and microRaman analyses suggest that the FeNi metal and magnetite (Fe₂O₃FeO) also contain some hematite (Fe₂O₃). The FeNi has been partially oxidized (probably during capture), but on the basis of our experimental work with a light‐gas gun and microRaman analyses, we believe that some of the magnetite‐hematite mixtures may have originated on Wild 2. The terminal samples from track 121 also contain traces of sulfide and Mg‐rich silicate minerals. Our results show an unequilibrated mixture of reduced and oxidized Fe‐bearing minerals in the Wild 2 samples in an analogous way to mineral assemblages seen in carbonaceous chondrites and interplanetary dust particles. The samples contain some evidence for terrestrial contamination, for example, occasional Zn‐bearing grains and amorphous Fe oxide in track 121 for which evidence of a cometary origin is lacking.     

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.