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.     

GEMS,hydrated chondritic IDPs,CI‐matrix material: Sources of water in 81P/comet Wild 2

So far there is no conclusive evidence for water in the nucleus of 81P/comet Wild 2. Recently magnetite in collected Wild 2 samples was cited as proxy evidence for parent body aqueous alteration in this comet (Hicks et al. 2017 ). A potentional source for water of hydration would be layer silicates but unfortunately there is no record, neither texturally nor chemically, for hydrated layer silicates that survived hypervelocity impact in the Wild 2 samples. This paper reports large vesicles in the matrix of allocation C2044,2,41,2,5 from a volatile‐rich type B/C Stardust track. These vesicles were probably caused by boiling water that were generated when hydrated Wild 2 silicates impacted the near‐surface silica aerogel layer. Potential water sources were partially and fully hydrated GEMS (glass with embedded metal and sulfides) and CI carbonaceous chondrite materials among the earliest dusts that experienced hydration and icy‐body formation and long‐range transport and mixing with materials from across the solar system.     

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

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

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.     

Refractory materials in comet samples

Transmission electron microscope examination of more than 250 fragments, >1 μm from comet Wild 2 and a giant cluster interplanetary dust particle (GCP) of probable cometary origin has revealed four new calcium‐aluminum‐rich inclusions (CAIs), an amoeboid olivine aggregate (AOA), and an additional AOA or Al‐rich chondrule (ARC) object. All of the CAIs have concentric mineral structures and are composed of spinel + anorthite cores surrounded by Al,Ti clinopyroxenes and are similar to two previous CAIs discovered in Wild 2. All of the cometary refractory objects are of moderate refractory character. The mineral assemblages, textures, and bulk compositions of the comet CAIs are similar to nodules in fine‐grained, spinel‐rich inclusions (FGIs) found in primitive chondrites and like the nodules may be nebular condensates that were altered via solid–gas reactions in the solar nebula. Oxygen isotopes collected on one Wild 2 CAI also match FGIs. The lack of the most refractory inclusions in the comet samples may reflect the higher abundances of small moderately refractory CAI nodules that were produced in the nebula and the small sample sizes collected. In the comet samples, approximately 2–3% of all fragments larger than 1 μm, by number, are CAIs and nearly 50% of all bulbous Stardust tracks contain at least one CAI. We estimate that ~0.5 volume % of Wild 2 material and ~1 volume % of GCP is in the form of CAIs. ARCs and AOAs account for <1% of the Wild 2 and GCP grains by number.     

The future of Stardust science

Recent observations indicate that >99% of the small bodies in the solar system reside in its outer reaches—in the Kuiper Belt and Oort Cloud. Kuiper Belt bodies are probably the best‐preserved representatives of the icy planetesimals that dominated the bulk of the solid mass in the early solar system. They likely contain preserved materials inherited from the protosolar cloud, held in cryogenic storage since the formation of the solar system. Despite their importance, they are relatively underrepresented in our extraterrestrial sample collections by many orders of magnitude (~10¹³ by mass) as compared with the asteroids, represented by meteorites, which are composed of materials that have generally been strongly altered by thermal and aqueous processes. We have only begun to scratch the surface in understanding Kuiper Belt objects, but it is already clear that the very limited samples of them that we have in our laboratories hold the promise of dramatically expanding our understanding of the formation of the solar system. Stardust returned the first samples from a known small solar system body, the Jupiter‐family comet 81P/Wild 2, and, in a separate collector, the first solid samples from the local interstellar medium. The first decade of Stardust research resulted in more than 142 peer‐reviewed publications, including 15 papers in Science. Analyses of these amazing samples continue to yield unexpected discoveries and to raise new questions about the history of the early solar system. We identify nine high‐priority scientific objectives for future Stardust analyses that address important unsolved problems in planetary science.     

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

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

The smallest comet 81P/Wild 2 dust dances around the CI composition

The bulbous Stardust track #80 (C2092,3,80,0,0) is a huge cavity. Allocations C2092,2,80,46,1 nearest the entry hole and C2092,2,80,47,6 about 0.8 mm beneath the entry hole provide evidence of highly chaotic conditions during capture. They are dominated by nonvesicular low‐Mg silica glass instead of highly vesicular glass found deeper into this track which is consistent with the escape of magnesiosilica vapors generated from the smallest comet grains. The survival of delicate (Mg,Al,Ca)‐bearing silica glass structures is unique to the entry hole. Both allocations show a dearth of surviving comet dust except for a small enstatite, a low‐Ca hypersthene grain, and a Ti‐oxide fragment. Finding scattered TiO₂ fragments in the silica glass could support, but not prove, TiO₂ grain fragmentation during hypervelocity capture. The here reported dearth in mineral species is in marked contrast to the wealth of surviving silicate and oxide minerals deeper into the bulb. Both allocations show Fe‐Ni‐S nanograins dispersed throughout the low‐Mg silica glass matrix. It is noted that neither comet Halley nor Wild 2 had a CI bulk composition for the smallest grains. Using the analogs of interplanetary dust particles (IDPs) and cluster IDPs it is argued that a CI chondritic composition requires the mixing of nonchondritic components in the appropriate proportions. So far, the fine‐grained Wild 2 dust is biased toward nonchondritic ferromagnesiosilica materials and lacking contributions of nonchondritic components with Mg‐Fe‐Ni‐S[Si‐O] compositions. To be specific, “Where are the GEMS”? The GEMS look‐alike found in this study suggests that evidence of GEMS in comet Wild 2 may still be found in the Stardust glass.     

Nebular mixing constrained by the Stardust samples

Abstract— Using X‐ray microprobe analysis of samples from comet Wild 2 returned by the Stardust mission, we determine that the crystalline Fe‐bearing silicate fraction in this Jupiter‐family comet is greater than 0.5. Assuming this mixture is a composite of crystalline inner solar system material and amorphous cold molecular cloud material, we deduce that more than half of Wild 2 has been processed in the inner solar system. Several models exist that explain the presence of crystalline materials in comets. We explore some of these models in light of our results.     

A cometary aggregate interplanetary dust particle as an analog for comet Wild 2 grain chemistry preserved in silica‐rich Stardust glass

Abstract— Many of the nanometer‐scale grains from comet 81P/Wild 2 did not survive hypervelocity capture. Instead, they melted and interacted with silica melt derived from the aerogel used by the Stardust mission. Their petrological properties were completely modified, but their bulk chemistry was preserved in the chemical signatures of mostly vesicular Si‐rich glass with its typical Fe‐Ni‐S compound inclusions. Chondritic aggregate IDP L2011A9 that experienced atmospheric pre‐entry thermal modification was selected as an analog to investigate these Wild 2 chemical signatures. The chemical, petrologic, and mineralogical properties of the individual constituents in this aggregate IDP are presented and used to match the chemical signatures of these Wild 2 grains. Mixing of comet material and pure silica, which is used in a diagram that recognizes this mixing behavior, is used to constrain the probable petrologic and minerals that caused the Wild 2 signatures. The Wild 2 nanometer‐scale grain signatures in Si‐rich glass allocations from three different deceleration tracks resembled mixtures of ultrafine‐grained principal components and dense agglomerate‐like material, Mg‐rich silicates (<500 nm) and Fe,Ni‐sulfides (<100 nm), and Si‐rich amorphous material. Dust resembling the mixed matrix of common chondritic aggregate IDPs was present in Jupiter‐family comet Wild 2.     

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.     

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.     

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.     

Short-period Jupiter family comets after Stardust

The NASA Stardust mission has provided for laboratory study an extensive data set of cometary dust of known provenance (from comet 81P/Wild 2) yielding detailed insights into the composition of the comet. Combined with the results of data from other missions to short-period Jupiter family comets (JFC), this has greatly deepened the understanding of such objects. If depressions on the surface of comet 81P/Wild 2 are all taken as evidence of impact cratering, their number suggests a long occupancy in the outer region of the Solar System. The dust from comet 81P/Wild 2 has been shown to be heavily deficient in pre-Solar grains and rich in materials formed at high temperatures in the inner Solar System. Although it is too early to know if this is typical of JFC, it does argue for rapid and thorough mixing of materials in the disk on timescales related to comet formation, and may also suggest outward migration of small icy bodies after their formation. Thus, instead of providing mainly new knowledge of the pre-Solar materials expected to be rich in comets, Stardust and comet 81P/Wild 2 have instead focussed attention on large-scale transport processes during the critical period when cometary parent bodies were forming in the early Solar System.     

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.     

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.     

Searching for calcium‐aluminum‐rich inclusions in cometary particles with Rosetta/COSIMA

The calcium‐aluminum‐rich inclusions (CAIs) found in chondritic meteorites are probably the oldest solar system solids, dating back to 4567.30 ± 0.16 million years ago. They are thought to have formed in the protosolar nebula within a few astronomical units of the Sun, and at a temperature of around 1300 K. The Stardust mission found evidence of CAI‐like material in samples recovered from comet Wild 2. The appearance of CAIs in comets, which are thought to be formed at lower temperatures and larger distances from the Sun, is only explicable if some mechanism allows the efficient transfer of such objects from the inner solar nebula to the outer solar nebula. Such mechanisms have been proposed such as an X‐wind or turbulence. In this work, particles collected from within the coma of comet 67P/Churyumov–Gerasimenko are examined for compositional evidence of the presence of CAIs. COSIMA (the Cometary Secondary Ion Mass Analyzer) uses secondary ion mass spectrometry to analyze the composition of cometary dust captured on metal targets. While CAIs can have a radius of centimeters, they are more typically a few hundred microns in size, and can be smaller than 1 μm, so it is conceivable that particles visible on COSIMA targets (ranging in size from about 10 μm to hundreds of microns) could contain CAIs. Using a peak fitting technique, the composition of a set of 13 particles was studied, looking for material rich in both calcium and aluminum. One such particle was found.     

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).     

Fine‐grained material associated with a large sulfide returned from Comet 81P/Wild 2

In a consortium analysis of a large particle captured from the coma of comet 81P/Wild 2 by the Stardust spacecraft, we report the discovery of a field of fine‐grained material (FGM) in contact with a large sulfide particle. The FGM was partially located in an embayment in the sulfide. As a consequence, some of the FGM appears to have been protected from damage during hypervelocity capture in aerogel. Some of the FGM particles are indistinguishable in their characteristics from common components of chondritic‐porous interplanetary dust particles, including glass with embedded metals and sulfides and equilibrated aggregates. The sulfide exhibits surprising Ni‐rich lamellae, which may indicate that this particle experienced a long‐duration heating event after its formation but before incorporation into Wild 2.     

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.