Glass With Embedded Metal And Sulfides Research Articles

Petrographic and chemical characterization and carbon and nitrogen isotopic compositions of cometary IDPs and their GEMS amorphous silicates

GEMS (glass with embedded metal and sulfides) are the dominant carrier of amorphous silicates in anhydrous interplanetary dust particles (IDPs) and one of the most suitable materials to study early solar system processes. Amorphous silicates in 105 GEMS from eight IDPs were analyzed regarding texture and chemical composition to reassess GEMS formation theories and genetic relationships to amorphous silicate material in meteorites. Petrography of bulk IDPs was investigated to understand GEMS’ relationships to other IDP components. Furthermore, carbon and nitrogen isotopic compositions were measured. Nearly all GEMS are aggregates of several subgrains with variable amount of nanophase inclusions and different Mg- and Si-contents, while single GEMS are rare. The subgrains within aggregates are typically surrounded by one or more carbon rims with high density. The chemical compositions of GEMS amorphous silicates are subsolar for all major element/Si ratios but exhibit wide heterogeneity. This is not influenced by silicon oil from the capturing process of IDPs as assumed before, as a penetration of the silicon oil is excluded by high resolution EELS (electron energy loss spectroscopy) areal density maps of silicon. Furthermore, low Fe-content in GEMS amorphous silicates shows that these are not altered by aqueous activity on the parent body as it is the case for amorphous silicate material in primitive meteorites. The subsolar element/Si ratios and the wide chemical heterogeneity point to a non-equilibrium fractional condensation origin either in the early solar nebula or in a circumstellar environment and are not in agreement with homogenization via sputtering in the ISM. The close association with carbon around GEMS subgrains and as double-rims around GEMS aggregates argue for a multi-step aggregation after formation of the smallest GEMS subgrains in the ISM or the early solar nebula. Carbon acting as matrix material connecting GEMS and other IDP components has lower areal density as seen from carbon EELS areal density maps and isotopic anomalies varying at the nanometer scale, pointing to different origins and processing of materials to varying extent or at changing temperatures.To balance GEMS’ subsolar element/Si ratios, a supersolar component in IDPs was assumed to account for the overall chondritic composition of bulk IDPs. Nevertheless, our bulk IDP analyses revealed subsolar, but variable, element/Si ratios for complete particles as well, depending on type and amount of mineral phases in each particle. Pyroxenes in the investigated particles can occur as elongated euhedral crystals, but are overall rare. The dominant crystalline fraction in the investigated IDP samples are equilibrated aggregates (EAs) that show the same chemical compositions as GEMS, indicating that the EAs are recrystallized GEMS grains and formed after GEMS formation as secondary phases.

Phyllosilicates with embedded Fe‐based nanophases in Ryugu and Orgueil

AbstractSamples were recently collected from the carbonaceous asteroid (162173) Ryugu, by the Japan Aerospace Exploration Agency (JAXA) Hayabusa2 mission. They resemble CI chondrites material, thus showing clear evidence of extensive aqueous alteration attested by the widespread presence of a mixture of serpentine and saponite. We present here a scanning transmission electron microscopy study of the Ryugu dominant lithology of the phyllosilicate matrix at the nanometer scale, which we compare with that of the Orgueil CI chondrite. In both objects, the phyllosilicates are of comparable nature and texture, consisting of a mixture of small‐sized crystallites of serpentine and saponite. At the micrometer scale or less, the texture is an alternation of fine and coarse domains. The fine‐grained regions are dominated by saponite. In Ryugu, they enclose numerous Fe,Ni nanosulfides, whereas in Orgueil, S‐ and Ni‐rich ferrihydrite is abundant. The coarse‐grained regions contain more serpentine and no or little Fe,Ni sulfides or ferrihydrite. Scanning transmission x‐ray microscopy at the Fe‐L3 edge also reveals that iron valency of phyllosilicates is higher and more homogeneous in Orgueil (~70% Fe3+) than in Ryugu (<50% Fe3+). We interpret the observed textures as being mostly a consequence of aqueous alteration, likely resulting from the replacement by phyllosilicates of submicrometric components, initially agglomerated by a primary accretion. The fine‐grained domains may result from the replacement of GEMS (GEMS—glass with embedded metal and sulfides) objects or from other types of nanometric assemblages of silicate and Fe‐based nanophases. On the other hand, the coarse‐grained regions may correspond to the replacement of anhydrous crystalline silicates of the olivine and pyroxene type. The major difference is the presence of Fe,Ni sulfides in Ryugu and of ferrihydrite and higher iron valency of phyllosilicates in Orgueil. This might be due to long‐term terrestrial weathering that would have destabilized the nanosulfides. We also explore an alternative scenario involving more oxidizing hydrothermal conditions on the Orgueil parent body.

On the provenance of GEMS, a quarter century post discovery

The provenance of GEMS (glass with embedded metal and sulfides) in cometary type interplanetary dust particles is investigated using analytical scanning transmission electron microscopy and secondary ion mass spectrometry. We review the current state of knowledge and closely examine the densities, elemental compositions and distributions, iron oxidation states, and isotopic compositions of a subset of GEMS in chondritic porous interplanetary dust. We find that GEMS are underdense with estimated densities that are 35–65% of compositionally equivalent crystalline aggregates. GEMS low densities result in a lower contribution to the bulk compositions of IDPs than has been assumed based on their volume fraction. We also find that element/Si ratios, assumed to be primary (indigenous), are instead perturbed by contamination and secondary alteration, including pulse heating during atmospheric entry. Fe in pyrrhotite inclusions was oxidized and Mg, S, Ca, and Fe were depleted relative to lithophile Al and Si, resulting in reduction in element/Si ratios. Because they trap outgassing elements, Fe-rich oxide rims that formed on the surface of GEMS are serendipitous “witness plates” to the changes in composition that accompany atmospheric entry. As a result of alteration, GEMS elemental compositions cannot reliably inform about their provenance. Except for highly anomalous oxygen isotope ratios measured in some large GEMS grains that indicate a contribution from circumstellar dust, oxygen isotope compositions are generally poor indicators of provenance. Prior work indicates that most GEMS fall close to the terrestrial oxygen isotope composition, which, however, does not exclude a presolar interstellar origin. Nitrogen isotopic compositions are more diagnostic. Elevated 15N/14N ratios indicate that GEMS accreted in conjunction with formation of organic matter by ion–molecule reactions in a cold (<50 K) presolar environment like the extreme outer nebula or interstellar medium. Considering all observations, we conclude that GEMS are most likely processed interstellar silicates.

Condensation of cometary silicate dust using an induction thermal plasma system

Glass with embedded metal and sulfides (GEMS), the major components of chondritic-porous interplanetary dust particles (CP-IDPs), is one of the most primitive materials in the Solar System and may be analogous to the amorphous silicate dust observed in various astronomical environments. Mineralogical characteristics of GEMS should reflect their formation process and condition. In this study, synthetic experiments in the sulfur-bearing system of Fe–Mg–Si–O–S were performed with a systematic change in redox conditions using thermal plasma systems to reproduce the mineralogy and textures of GEMS. The resulting condensates were composed of amorphous silicates with Fe-bearing nano-inclusions. The Fe content and texture in the amorphous silicates as well as the mineral phases of the nanoparticles correlate with redox conditions. Fe dissolved in the amorphous silicate as FeO in oxidizing conditions formed Fe-metal nanoparticles in intermediate redox conditions, and gupeiite (Fe3 Si) nanoparticles in reducing conditions. In intermediate to reducing redox conditions, Fe-poor amorphous silicate formed a biphasic texture with Mg- and Si-rich regions, indicating liquid immiscibility during the melt phase. Most Fe-metal particles were surrounded by FeS and formed on the surface of amorphous silicate grains. Condensates produced in intermediate to slightly reducing redox conditions resemble GEMS in that they have similar mineral assemblages and chemical compositions to amorphous silicate, except that the Fe-metal grains are absent from the interior of the amorphous silicate grains. This textural difference can be explained by the sulfidation at high temperatures in this study, in contrast to sulfidation occurring at low temperatures in the presence of H2 in natural GEMS formation. Based on the two-liquid structures observed in the experimental products and in GEMS, also recognized in infrared spectra, we propose that GEMS condensed as silicate melt under limited redox conditions followed by incorporation of multiple metal grains into the silicate melt or by aggregation of coreshell structured grains before sulfidation of the metallic iron. Condensates produced in oxidizing conditions are similar to GEMS-like material in the matrices of primitive carbonaceous chondrite meteorites, indicating the possibility that they form by direct condensation from nebula gas in relatively oxidizing conditions compared to GEMS.

Three-dimensional observation of GEMS grains: Their high-temperature condensation origin

GEMS (Glass with Embedded Metal and Sulfides) grains found in interplanetary dust particles are considered one of the most primitive materials in the Solar System, yet questions remain on how they formed. It has been suggested that GEMS grains are products of radiation processing and amorphization of sulfide and silicate mineral grains in the interstellar medium. Alternatively, GEMS grains are proposed to be disequilibrium condensation products in late-stage protosolar disks. We examined the 3D distributions of elements and inclusions within GEMS grains using TEM (transmission electron microscopic)-tomography to better constrain their possible formation processes. We found some core–shell particles composed of metals and amorphous silicates and observed a binary distribution of Mg/Si in amorphous silicates of GEMS grains. These properties are highly similar to the features of experimental condensation products. Furthermore, the location of sulfides only on the surface of GEMS and their larger sizes than metals are also consistent with the condensation experiments, where sulfides formed by sulfidation of metal grains with S-bearing gas species. Textures showing aggregation and possible coalescence of primary grains were also observed. Therefore, we conclude that GEMS grains are condensates from gas at high temperatures and some of them were aggregated.

Condensation of cometary silicate dust using an induction thermal plasma system

Glass with embedded metal and sulfides (GEMS) is a major component of chondritic porous interplanetary dust particles. Although GEMS is one of the most primitive components in the Solar System, its formation process and conditions have not been constrained. We performed condensation experiments of gases in the system of Mg–Si–O (MgSiO3 composition) and of the S-free CI chondritic composition (Si–Mg–Fe–Na–Al–Ca–Ni–O system) in induction thermal plasma equipment. Amorphous Mg-silicate particles condensed in the experiments of the Mg–Si–O system, and their grain size distribution depended on the experimental conditions (mainly partial pressure of SiO). In the CI chondritic composition experiments, irregularly shaped amorphous silicate particles of less than a few hundred nanometers embedded with multiple Fe–Ni nanoparticles of ≤20 nm were successfully synthesized. These characteristics are very similar to those of GEMS, except for the presence of FeSi instead of sulfide grains. We propose that the condensation of amorphous silicate grains smaller than a few tens of nanometers and with metallic cores, followed by coagulation, could be the precursor material that forms GEMS prior to sulfidation.

Search for meteoritic GEMS II: Comparison of inclusions in amorphous silicates from the Paris chondrite and from anhydrous chondritic interplanetary dust particles

Amorphous silicates containing abundant nano-inclusions have been reported in the Paris CM chondrite (Leroux et al., 2015). They have chemical and morphological similarities to glass with embedded metal and sulfides (GEMS) found in interplanetary dust particles (IDPs) and micrometeorites believed to originate from comets. We used scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS) and nanodiffraction to study the chemistry and mineralogy of these inclusions in order to understand the origin of the GEMS-like material in Paris and its possible relationships to other materials found in primitive chondritic materials including IDP GEMS. EDS and diffraction analyses indicate compositional and mineralogical differences between the nanophase inclusions in cometary GEMS and Paris GEMS-like material. Metal inclusions are notably absent within Paris amorphous silicate. Ni-rich sulfides, including pentlandite, are common in even the least altered matrix material of Paris, while they are absent in GEMS-bearing IDPs and Ultracarbonaceous Antarctic Micrometeorites (UCAMMs). From examination of the inclusions, we cannot yet confirm or refute the possibility that GEMS-like material in Paris is related to cometary GEMS. The distinct compositions and mineralogy of the Paris material may be due to aqueous alteration of cometary GEMS precursors, but they may also denote an independent origin for meteoritic GEMS-like assemblages.

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

AbstractSo 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. ). 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.

Multiple generations of grain aggregation in different environments preceded solar system body formation

The solar system formed from interstellar dust and gas in a molecular cloud. Astronomical observations show that typical interstellar dust consists of amorphous (a-) silicate and organic carbon. Bona fide physical samples for laboratory studies would yield unprecedented insight about solar system formation, but they were largely destroyed. The most likely repositories of surviving presolar dust are the least altered extraterrestrial materials, interplanetary dust particles (IDPs) with probable cometary origins. Cometary IDPs contain abundant submicron a-silicate grains called GEMS (glass with embedded metal and sulfides), believed to be carbon-free. Some have detectable isotopically anomalous a-silicate components from other stars, proving they are preserved dust inherited from the interstellar medium. However, it is debated whether the majority of GEMS predate the solar system or formed in the solar nebula by condensation of high-temperature (>1,300 K) gas. Here, we map IDP compositions with single nanometer-scale resolution and find that GEMS contain organic carbon. Mapping reveals two generations of grain aggregation, the key process in growth from dust grains to planetesimals, mediated by carbon. GEMS grains, some with a-silicate subgrains mantled by organic carbon, comprise the earliest generation of aggregates. These aggregates (and other grains) are encapsulated in lower-density organic carbon matrix, indicating a second generation of aggregation. Since this organic carbon thermally decomposes above ∼450 K, GEMS cannot have accreted in the hot solar nebula, and formed, instead, in the cold presolar molecular cloud and/or outer protoplanetary disk. We suggest that GEMS are consistent with surviving interstellar dust, condensed in situ, and cycled through multiple molecular clouds.

Formation of an ultracarbonaceous Antarctic micrometeorite through minimal aqueous alteration in a small porous icy body

A comprehensive study of the organic chemistry and mineralogy of an ultracarbonaceous micrometeorite (UCAMM D05IB80) collected from near the Dome Fuji Station, Antarctica, was carried out to understand the genetic relationship among organic materials, silicates, and water. The micrometeorite is composed of a dense aggregate of ∼5µm-sized hollow ellipsoidal organic material containing submicrometer-sized phases such as glass with embedded metal and sulfides (GEMS) and mineral grains. There is a wide area of organic material (∼15×15μm) in its interior. Low-Ca pyroxene is much more abundant than olivine and shows various Mg/(Mg+Fe) ratios ranging from ∼1.0 to 0.78, which is common to previous works on UCAMMs. By contrast, GEMS grains in this UCAMM have unusual chemical compositions. They are depleted in both Mg and S, which suggests that these elements were leached out from the GEMS grains during very weak aqueous alteration, without the formation of phyllosilicates.The organic materials have two textures—smooth and globular with an irregular outline—and these are composed of imine, nitrile and/or aromatic nitrogen heterocycles, and amide. The ratio of nitrogen to carbon (N/C) in the smooth region of the organics is ∼0.15, which is five times higher than that of insoluble organic macromolecules in types 1 and 2 carbonaceous chondritic meteorites. In addition, the UCAMM organic materials are soluble in epoxy and are thus hydrophilic; this polar nature indicates that they are very primitive. The surface of the material is coated with an inorganic layer, a few nanometers thick, that consists of C, O, Si, S, and Fe. Sulfur is also contained in the interior, implying the presence of organosulfur moieties. There are no isotopic anomalies of D, 13C, or 15N in the organic material.Interstellar photochemistry alone would not be sufficient to explain the N/C ratio of the UCAMM organics; therefore, we suggest that a very small amount of fluid on a comet must have been necessary for the formation of the UCAMM. The GEMS grains depleted in Mg and S in the UCAMM prove a very weak degree of aqueous alteration; weaker than that of carbonaceous chondrites. Short-duration weak alteration probably caused by planetesimal shock locally melted cometary ice grains and released water that dissolved the organics; the fluid would likely have not mobilized because of the very low thermal conductivity of the porous icy body. This event allowed the formation of the large organic puddle of the UCAMM, as well as organic matter sulfurization, formation of thin membrane-like layers of minerals, and deformation of organic nanoglobules.

GEMS-like material in the matrix of the Paris meteorite and the early stages of alteration of CM chondrites

The Paris meteorite is a weakly altered CM chondrite that has been discovered recently (Hewins et al., 2014). Its matrix offers the opportunity to search for well-preserved pristine pre-accretional material, as well as to study the earliest stages of aqueous alteration in the CM parent body. The study of the matrix of Paris has been conducted by analytical transmission electron microscopy on focused ion beam sections extracted from matrix areas showing different degrees of aqueous alteration.The least altered matrix sample consists of amorphous silicate grains, a few hundreds of nm in size, separated from one another by an abundant porosity. The amorphous silicates enclose numerous Fe-sulfide nanograins and their average composition is close to the chondritic composition. They share many similarities with GEMS (glass with embedded metal and sulfides) grains present in chondritic-porous interplanetary dust particles and with primitive type 3.0 carbonaceous chondrites. This first discovery of GEMS-like texture in a CM chondrite suggests that GEMS grains could have been the building blocks of the CM matrices.In more aqueously altered samples, pronounced microstructural heterogeneities were detected at the micrometer scale. The matrix consists mostly of a mixture of amorphous material and Fe-rich, spongy to fine-fibrous, poorly crystalline phyllosilicates. The porosity fraction is significantly reduced and the mixed amorphous-fibrous material frequently forms a continuous groundmass. The close association between these two material types suggests a replacement mechanism due to aqueous alteration. Chemical compositions correlate strongly with the microstructure. The amorphous material has a composition close to the chondritic value while the fine-fibrous phyllosilicate material is Fe-enriched. This Fe enrichment is found to be continuous from weakly to more heavily altered areas, in which the fibrous morphology is coarser and better crystalline. Cronstedtite with intercalated tochilinite is also found, but in pore spaces. This chemical evolution, concomitant with the maturation of the phyllosilicates, demonstrates that the early aqueous fluids that interacted with silicates in the matrix were enriched in Fe. This composition is probably the consequence of the preferential dissolution of metal and iron sulfides during the first stages of alteration. The enrichment of phyllosilicates in Mg seen in more altered CM chondrites is not observed in Paris.

REDUCTION EXPERIMENT OF FeO-BEARING AMORPHOUS SILICATE: APPLICATION TO ORIGIN OF METALLIC IRON IN GEMS

Glass with embedded metal and sulfides (GEMS) are amorphous silicates included in anhydrous interplanetary dust particles (IDPs) and can provide information about material evolution in our early solar system. Several formation processes for GEMS have been proposed so far, but these theories are still being debated. To investigate a possible GEMS origin by reduction of interstellar silicates, we synthesized amorphous silicates with a mean GEMS composition and performed heating experiments in a reducing atmosphere. FeO-bearing amorphous silicates were heated at 923 K and 973 K for 3 hr, and at 1023 K for 1-48 hr at ambient pressure in a reducing atmosphere. Fe grains formed at the interface between the silicate and the reducing gas through a reduction. In contrast, TEM observations of natural GEMS show that metallic grains are uniformly embedded in amorphous silicates. Therefore, the present study suggests that metallic inclusions in GEMS could not form as reduction products and that other formation process such as condensation or irradiation are more likely.

How and where did GEMS form?

In the paper “On the Origins of GEMS”Keller and Messenger (2011) present the results of a study of GEMS (glass with embedded metal and sulfides) in chondritic porous interplanetary dust particles (CP IDPs). They find that non-solar oxygen isotopic abundances are detectable in a few typically the largest GEMS, confirming that they are surviving presolar amorphous silicates derived from the interstellar medium (ISM). They argue that those without detectable anomalies, the majority, formed in the solar system even though they are otherwise identical to the anomalous GEMS. Their conclusion is based on element-to-Si ratios, but GEMS-rich CP IDPs are collected, stored in and permanently contaminated with silicone oil. They are also thermally unstable and chemically reactive during atmospheric entry, which further modifies element-to-Si ratios. Both of the approaches employed to argue negligible silicone oil contamination are problematical: First, carbon is used as a tracer for silicone oil contamination, but carbon is both native to the IDPs and introduced throughout the sample collection and preparation processes. Second, the absence of an ∼8μm infrared (IR) feature is cited, based on refitting of previously published spectra using a polynomial spline.

A NanoSIMS and Raman spectroscopic comparison of interplanetary dust particles from comet Grigg‐Skjellerup and non‐Grigg Skjellerup collections

Abstract–Interplanetary dust particles (IDPs) are the most primitive extraterrestrial material available for laboratory studies and may, being likely of cometary origin, sample or represent the unaltered starting material of the solar system. Here we compare IDPs from a “targeted” collection, acquired when the Earth passed through the dust stream of comet 26P/Grigg‐Skjellerup (GSC), with IDPs from nontargeted collections (i.e., of nonspecific origin). We examine both sets to further our understanding of abundances and character of their isotopically anomalous phases to constrain the nature of their parent bodies. We identified ten presolar silicates, two oxides, one SiC, and three isotopically anomalous C‐rich grains. One of seven non‐GSC IDPs contains a wealth of unaltered nebula material, including two presolar silicates, one oxide, and one SiC, as well as numerous δD and δ15N hotspots, demonstrating its very pristine character and suggesting a cometary origin. One of these presolar silicates is the most17O‐rich discovered in an IDP and has been identified as a possible GEMS (glass with embedded metal and sulfides). Organic matter in an anhydrous GSC IDP is extremely disordered and, based on Raman spectral analyses, appears to be the most primitive IDP analyzed in this study, albeit only one presolar silicate was identified. No defining difference was seen between the GSC and non‐GSC IDPs studied here. However, the GSC collectors are expected to contain IDPs of nonspecific origin. One measure alone, such as presolar grain abundances, isotopic anomalies, or Raman spectroscopy cannot distinguish targeted cometary from unspecified IDPs, and therefore combined studies are required. Whilst targeted IDP populations as a whole may not show distinguishable parameters from unspecified populations (due to statistics, heterogeneity, sampling bias, mixing from other cometary sources), particular IDPs in a targeted collection may well indicate special properties and a fresh origin from a known source.

Transmission Electron Microscopy of CONCORDIA UltraCarbonaceous Antarctic MicroMeteorites (UCAMMs): Mineralogical properties

We performed mineralogical and petrographic studies of three UltraCarbonaceous Antarctic Micrometeorites (UCAMMs) by analytical transmission electron microscopy (TEM). The UCAMMs were identified in the CONCORDIA micrometeorite collection (2002 and 2006) recovered from central Antarctic snow, and are of probable cometary origin. UCAMMs are dominated by disordered carbonaceous matter that extends over surfaces of up to ∼90% of the particle. Embedded in this carbonaceous matter, we observed small and complex assemblages of fine-grained mineral phases, isolated minerals, glassy phases that resemble Glass with Embedded Metal and Sulfides (GEMS) that were first found in Interplanetary Dust Particles (IDPs), and rounded objects containing both glass and crystalline materials. The mineral assemblages are chondritic in composition, within a factor of 2. Crystalline materials represent at least 25% of mineral phases. This value is much larger than the upper limit of crystallinity measured in the diffuse interstellar medium (<2.2 wt%). Crystalline phases are dominated by low-Ca, Mg-rich pyroxenes, Mg-rich olivine and low-Ni Fe-sulfides. Exotic phases such as Mn-, Zn-rich sulfide and perryite have also been found as accessory minerals. The variety of high temperature mineral phases observed in UCAMMs is similar to that reported in chondritic porous IDPs and 81P/Wild 2 samples. The close association of high temperature crystalline phases with the low temperature carbonaceous matter in UCAMMs supports the hypothesis of a large-scale radial mixing in the early solar nebula. This new type of carbon-rich micrometeorites containing crystalline material provides the opportunity to analyze in situ, without any chemical processing, the association of materials formed at both low and high temperatures in the protoplanetary disk. A better knowledge of these samples is also important to prepare for future cometary missions, like ROSETTA in 2014.

On the origins of GEMS grains

From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation. We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1–6% of GEMS grains are surviving circumstellar grains. The remaining 94–99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the chemical compositions of GEMS grains are extremely heterogeneous and seem to rule out this possibility. Based on their solar isotopic compositions and their non-solar elemental compositions we propose that most GEMS grains formed in the nebula as late-stage non-equilibrium condensates.

Analytical SuperSTEM for extraterrestrial materials research

Abstract— Electron‐beam studies of extraterrestrial materials with significantly improved spatial resolution, energy resolution, and sensitivity are enabled using a 300 keV SuperSTEM scanning transmission electron microscope (STEM) with a monochromator and two spherical aberration correctors. The improved technical capabilities enable analyses previously not possible. Mineral structures can be directly imaged and analyzed with single‐atomic‐column resolution, liquids, and implanted gases can be detected, and UV‐VIS optical properties can be measured. Detection limits for minor/trace elements in thin (&lt;100 nm thick) specimens are improved such that quantitative measurements of some extend to the sub‐500 ppm level. Electron energy‐loss spectroscopy (EELS) can be carried out with 0.10–0.20 eV energy resolution and atomic‐scale spatial resolution such that variations in oxidation state from one atomic column to another can be detected. Petrographic mapping is extended down to the atomic scale using energy‐dispersive X‐ray spectroscopy (EDS) and energy‐filtered transmission electron microscopy (EFTEM) imaging. Technical capabilities and examples of the applications of SuperSTEM to extraterrestrial materials are presented, including the UV spectral properties and organic carbon K‐edge fine structure of carbonaceous matter in interplanetary dust particles (IDPs), X‐ray elemental maps showing the nanometer‐scale distribution of carbon within GEMS (glass with embedded metal and sulfides), the first detection and quantification of trace Ti in GEMS using EDS, and detection of molecular H2O in vesicles and implanted H2 and He in irradiated mineral and glass grains.

GEMS at the Galactic Cosmic-Ray Source

Galactic cosmic rays probably predominantly originate from shock-accelerated gas and dust in superbubbles. It is usually assumed that the shock-accelerated dust is quickly destroyed by sputtering. However, it may be that some of the dust can survive bombardment by the high-metallicity gas in the superbubble interior, and that some of that dust has been incorporated into solar system materials. Interplanetary dust particles (IDPs) contain enigmatic submicron components called GEMS (Glass with Embedded Metal and Sulfides). These GEMS have properties that closely match those expected of a population of surviving shock-accelerated dust at the GCR source (Westphal and Bradley in Astrophys. J. 617:1131, 2004). In order to test the hypothesis that GEMS are synthesized from shock-accelerated dust in superbubbles, we plan to measure the relative abundances of Fe, Zr, and Mo isotopes in GEMS using the new Resonance Ionization Mass Spectrometer at Argonne National Laboratory. If GEMS are synthesized from shock-accelerated dust in superbubbles, they should exhibit isotopic anomalies in Fe, Zr and Mo: specificially, enhancements in the r-only isotopes 96Zr and 100Mo, and separately in 58Fe, should be observed. We review also recent developments in observations of GEMS, laboratory synthesis of GEMS-like materials, and implications of observations of GEMS-like materials in Stardust samples.

Formation of Glass with Embedded Metal and Sulfides from Shock‐accelerated Crystalline Dust in Superbubbles

Interplanetary dust particles (IDPs) contain enigmatic submicron components called GEMS (glass with embedded metal and sulfides). The compositions and structures of GEMS indicate that they have been processed by exposure to ionizing radiation, but details of the actual irradiation environment(s) have remained elusive. Here we propose a mechanism and astrophysical site for GEMS formation that explains for the first time the following key properties of GEMS: they are stoichiometrically enriched in oxygen and systematically depleted in S, Mg, Ca, and Fe (relative to solar abundances); most have normal (solar) oxygen isotopic compositions; they exhibit a strikingly narrow size distribution (0.1-0.5 μm diameter); and some of them contain crystals within their silicate glass matrices. We show that the compositions, size distribution, and survival of relict crystals are inconsistent with amorphization by particles accelerated by diffusive shock acceleration. Instead, we propose that GEMS are formed from crystalline grains that condense in stellar outflows from massive stars in OB associations, are accelerated in encounters with frequent supernova shocks inside the associated superbubble (SB), and are implanted with atoms from the hot gas in the SB interior. We thus reverse the usual roles of target and projectile. Rather than being bombarded at rest by energetic ions, grains are accelerated and bombarded by a nearly monovelocity beam of atoms as viewed in their rest frame. Meyer, Drury, and Ellison have proposed that Galactic cosmic rays (GCRs) originate from ions sputtered from such accelerated dust grains. We suggest that GEMS are surviving members of a population of fast grains that constitute the long-sought source material for GCRs. Thus, representatives of the GCR source material may have been awaiting discovery in cosmic dust labs for the last 30 yr.

Mechanism of Formation of Glass with Embedded Metal and Sulfides

GEMS (glass with embedded metal and sulfides) grains in interplanetary dust particles (IDPs) were examined using 200 keV analytical transmission electron microscopy. The morphologies and crystallography of embedded relict grains reveal that GEMS are pseudomorphs formed by irradiation processing of crystals free-floating in space. Some GEMS retain a compositional and morphological memory of the crystal from which they formed. Pseudomorphism may rule out condensation, annealing, flash heating, or shock melting as alternative mechanisms of GEMS formation. A significant and often dominant fraction of the atoms in GEMS were sputter-deposited from other grains. Therefore, a normal (solar) isotopic composition is not a reliable indicator of whether GEMS formed in the solar system or in presolar interstellar or circumstellar environments.