Iron oxidation state in impact glass from the K/T boundary at Beloc,Haiti, by high‐resolution XANES spectroscopy

Abstract— We examined the local iron environment in nine impact glasses from the Cretaceous‐Tertiary (K/T) boundary section at Beloc, Haiti, which formed as the result of impact melting during the Chicxulub impact event. The samples have been analyzed by Fe K‐edge high‐resolution X‐ray absorption near edge structure (XANES) spectroscopy to obtain data on both the Fe oxidation state and the coordination number. The pre‐edge peak of our high‐resolution XANES spectra display noticeable variations indicative of significant changes in the Fe oxidation state spanning a wide range from about 20 to 75 mol% trivalent Fe. All data plot along the same trend, falling between two mixing lines joining a point calculated as the mean of a group of tektites studied so far (consisting of four‐ and five‐coordinated Fe²⁺) to ^[4]Fe³⁺ and ^[5]Fe³⁺, respectively. Thus, the XANES spectra can be interpreted as a mixture of ^[4]Fe²⁺, ^[5]Fe²⁺, ^[4]Fe³⁺, and ^[5]Fe³⁺. There is no evidence for six‐fold coordinated Fe; however, its presence in small amounts cannot be excluded from XANES data alone. Our observations can be explained by two possible scenarios: either these impact glasses formed under very reducing conditions and, because of their small size, were easily oxidized in air while still molten, or they formed under a variety of different oxygen fugacities resulting in different Fe oxidation states. In the first case, the oxidation state and coordination number would imply similar formation conditions as splash‐form tektites, followed by progressive oxidation.     

Yellow impact glass from the K/T boundary at Beloc (Haiti): XANES determination of the Fe oxidation state and implications for formation conditions

Abstract— We determined the iron oxidation state and coordination number in five samples of yellow impact glass from the Cretaceous‐Tertiary (K/T) boundary section at Beloc, Haiti, which formed as the result of impact melting during the Chicxulub impact event. The samples were analyzed by Fe K‐edge XANES spectroscopy and the results were compared with published data on eight black impact glasses and one high Si‐K impact spherule from the same impact layer. The pre‐edge peak of our high‐resolution XANES spectra displays evident variations indicative of significant changes in the Fe oxidation state, spanning a wide range from about 75 to 100 mole% Fe³⁺. Yellow K/T glasses have significantly higher Fe³⁺/(Fe²⁺ + Fe³⁺) ratios compared to black K/T impact glasses (from 20 to 75 mole% Fe³⁺) and high Si‐K glass (20 mole% Fe³⁺). In particular, all the pre‐edge peak data on these three types of impact glasses plot between two mixing lines joining a point calculated as the mean of a group of tektites studied so far (consisting of ^[4]Fe²⁺ and ^[5]Fe²⁺) to ^[4]Fe³⁺ and ^[5]Fe³⁺, respectively. Thus, the XANES spectra of the yellow K/T glasses can be interpreted as a mixture of ^[4]Fe^{2+, [5]}Fe^{2+, [4]}Fe³⁺, and ^[5]Fe³⁺. Our observations can be explained by a very large range of oxygen fugacity conditions during melt formation. Furthermore, there is a clear positive relationship between the Fe³⁺/(Fe²⁺ + Fe³⁺) ratio and the Ca content of these glasses, suggesting that the Fe oxidation state was influenced by the relative contribution of Ca‐sulfate‐ and Ca‐carbonate‐bearing sedimentary rocks at the impact site.     

Australasian microtektites from Antarctica: XAS determination of the Fe oxidation state

The Fe oxidation state and coordination number of 29 impact glass spherules recently recovered from the Transantarctic Mountains (Antarctica) have been determined by X‐ray absorption near edge structure (XANES) spectroscopy. Based on geochemical, isotopic, and fission track data, these spherules are considered as microtektites from the Australasian tektite/microtektite strewn field. Their find location is the farthest so far discovered from the possible source crater region, and their alkali content is the lowest compared with other published data on Australasian microtektite glasses. The Fe³⁺/(Fe²⁺+Fe³⁺) ratio, determined from the analysis of the pre‐edge peak energy position and integrated intensity, is below 0.1 (±0.04) for all the samples, and is comparable to that of most tektites and microtektites from the Australasian strewn field. Also, the pre‐edge peak integrated intensity, which is sensitive to the average Fe coordination geometry, is comparable to that of other Australasian microtektites reported in the literature. The agreement of the Fe oxidation state and coordination number, between the Transantarctic Mountain microtektites (TAM) and the Australasian tektites and microtektites, further confirms the impact origin of these glass spherules and provides an independent suggestion that they represent a major extension southeastward of the Australasian strewn field. The fact that similar redox conditions are observed in tektites and microtektites within the Australasian strewn field regardless of the distance from the source crater area (up to approximately 11000 km) could be an important constraint for better understanding the different processes affecting microtektite formation and transport. The fact that the Fe oxidation state of microtektites does not increase with distance, as in the case of North American microtektites, means that thermal and redox histories of Australasian and TAM microtektites could differ significantly from those of North American microtektites.     

Brownish inclusions and dark streaks in Libyan Desert Glass: Evidence for high‐temperature melting of the target rock

Abstract– Dark streaks and different types of inclusions in Libyan Desert Glass (LDG) collected from the LDG strewn field in Egypt were investigated. Rare transparent spherules enclosed in the glassy matrix are characterized by concentric cracks, irregular internal cracks, intense twinning, and considerable amounts of Ti and Al. Raman spectra show that the spherules are α‐cristobalite. Their occurrence together with lechatelierite indicates quick heating of the source rock to at least 1550 °C, followed by rapid quenching leading to crystallization of β‐cristobalite, which upon cooling inverted into α‐cristobalite. Brownish inclusions are irregularly shaped, elongated objects with smooth contacts to the surrounding glass. They contain small roundish to elliptical droplets, and a few larger angular grains, which compositionally and according to their Raman spectra most closely resemble low‐Ca, Al‐rich orthopyroxene. Composition and texture of the orthopyroxene suggest that the brownish inclusions formed by incomplete melting of an Al‐rich orthopyroxene bearing precursor, e.g., mafic phases present in desert surface sands or also of orthopyroxene‐bearing granulite dykes in the LDG target. Experimental data on Ca‐poor enstatite also support that the inclusions were heated to about 1550 °C. Analyses of dark streaks in LDG reveal high abundances of Al, Ti, Mn, Cr, Fe, and Ni and a pronounced correlation between the abundances of Cr, Mn, Fe, and Ni. As the Fe/Ni, Mn/Ni, and Cr/Ni ratios are all clearly nonchondritic, the source of this material is most likely terrestrial and the dark streaks studied here represent a different type of schlieren compared to those which contain a meteoritic component. These findings suggest LDG formation during a short high‐temperature event. Melting of Al‐rich orthopyroxene bearing target material seems to suggest an asteroid impact rather than a near‐surface airburst.     

Determination of the Fe oxidation state of the Chassigny kaersutite: A microXANES spectroscopic study

Abstract— In order to elucidate the formation of low‐H kaersutites in Martian meteorites, the Fe³⁺/ΣFe ratio of Chassigny kaersutites in magmatic inclusions was directly determined by the synchrotron microXANES analysis. XANES analysis for standard kaersutites with known Fe³⁺/ΣFe ratios shows a linear relationship between centroid energy positions of XANES pre‐edge spectra and the Fe³⁺/ΣFe ratio. Based on the linear relationship, the Fe³⁺/ΣFe ratio of Chassigny kaersutites is estimated to be about 0.05. The low Fe³⁺/ΣFe ratio clearly suggests that low‐H kaersutites in Chassigny are not likely to be formed by the oxidation‐dehydrogenation reactions. The low‐H content of the Chassigny kaersutites is mainly due to the presence of a Ti oxy‐component.     

Strontium and neodymium isotopic study of Libyan Desert Glass: Inherited Pan‐African age signatures and new evidence for target material

Abstract— Libyan Desert Glass (LDG) is an impact‐related, natural glass of still unknown target material. We have determined Rb‐Sr and Sm‐Nd isotopic ratios from seven LDG samples and five associated sandstones from the LDG strewn field in the Great Sand Sea, western Egypt. Planar deformation features were recently detected in quartz from these sandstones. ⁸⁷Sr/⁸⁶Sr ratios and ?‐Nd values for LDG range between 0.71219 and 0.71344, and between –16.6 and –17.8, respectively, and hence are distinct from the less radiogenic ⁸⁷Sr/⁸⁶Sr ratios of 0.70910–0.71053 and ?‐Nd values from –6.9 to –9.6 for the local sandstones from the LDG strewn field. Previously published isotopic ratios from the Libyan BP and Oasis crater sandstones are generally incompatible with our LDG values. LDG formation undoubtedly occurred at 29 Ma, but neither the Rb‐Sr nor the Sm‐Nd isotopic system were rehomogenised during the impact event, as we can deduce from Pan‐African ages of ?540 Ma determined from the regression lines from a total of 14 LDG samples from this work and the literature. Together with similar Sr and Nd isotopic values for LDG and granitoid rocks from northeast Africa west of the Nile, these findings point to a sandy matrix target material for the LDG derived from a Precambrian crystalline basement, ruling out the Cretaceous sandstones of the former “Nubian Group” as possible precursors for LDG.     

δ18O and chemical composition of Libyan Desert Glass,country rocks,and sands: New considerations on target material

Oxygen isotope and chemical measurements were carried out on 25 samples of Libyan Desert Glass (LDG), 21 samples of sandstone, and 3 of sand from the same area. The δ¹⁸O of LDG samples range from 9.0‰ to 11.9‰ (Vienna Standard Mean Ocean Water [VSMOW]); some correlations between isotope data and typological features of the LDG samples are pointed out. The initial δ¹⁸O of a bulk parent material may be slightly increased by fusion due to the loss of isotopically light pore water with no isotope exchange with oxygen containing minerals. Accordingly, the δ¹⁸O of the bulk parent material of LDG may have been about 9.0 ± 1‰ (VSMOW). The measured bulk sandstone and sand samples have δ¹⁸O values ranging from 12.6‰ to 19.5‰ and are consequently ruled out as parent materials, matching the results of previous studies. However, separated quartz fractions have δ¹⁸O values compatible with the LDG values suggesting that the modern surface sand inherited quartz from the target material. This hypothesis fits previous findings of lechatelierite and baddeleyite in these materials. As the age of the parent material reported in previous studies is Pan‐African, we measured the δ¹⁸O values of bulk rock and quartz from intrusives of Pan‐African age and the results obtained were compatible with the LDG values. The main element abundances (Fe, Mg, Ca, K, Na) in our LDG samples conform to previous estimates; Fe, Mg, and K tend to be higher in heterogeneous samples with dark layers. The hypothesis of a low‐altitude airburst involving silica‐rich surface materials deriving from weathered intrusives of Pan‐African age, partially melted and blown over a huge surface by supersonic winds matches the results obtained.     

Effect of hot desert weathering on the bulk‐rock iron isotope composition of L6 and H5 ordinary chondrites

Abstract– Although iron isotopes are increasingly used for meteorites studies, no attempt has been made to evaluate the effect of terrestrial weathering on this isotopic tracer. We have thus conducted a petrographic, chemical, and iron isotopic study of equilibrated ordinary chondrites (OC) recovered from hot Moroccan and Algerian Saharan deserts environment. As previously noticed, we observe that terrestrial desertic weathering is characterized by the oxidation of Fe‐Ni metal (Fe⁰), sulfide and Fe²⁺ occurring in olivine and pyroxene. It produces Fe‐oxides and oxyhydroxides that partially replace metal, sulfide grains and also fill fractures. The bulk chemical compositions of the ordinary chondrites studied show a strong Sr and Ba enrichment and a S depletion during weathering. Bulk meteoritic iron isotope compositions are well correlated with the degree of weathering and S, Sr, and Ba contents. Most weathered chondrites display the heaviest isotopic composition, by up to 0.1‰, which is of similar magnitude to the isotopic variations resulting from meteorite parent bodies’ formation and evolution. This is probably due to the release of isotopically light Fe²⁺ to waters on the Earth’s surface. Hence, when subtle Fe isotopic effects have to be studied in chondrites, meteorites with weathering grade above W2 should be avoided.     

Alkali‐feldspathic material entrained in Fe,S‐rich veins in a monomict ureilite

Abstract— The Elephant Moraine (EET) 96001 ureilite contains a remarkable diversity of feldspars, which occur as tiny (no more than 60 μm maximum dimension) grains within a few Fe,S‐rich (now weathered to mostly Fe oxide) veins. Molar S: Fe ratio in the veins averages 0.08 ± 0.02. The veins meander and feature large fluctuations in apparent width; they appear to have entered this monomict breccia by a gentle, percolative process, not by violent impact injection. The feldspars are accompanied by a diverse suite of K‐rich (and generally also Ti‐rich) feldspathic glasses, and also major proportions of silica and pyroxene, which is largely fassaitic. A rhönite‐like phase is also found, and, as inclusions in one of the fassaites, a Cr‐poor spinel‐like phase. The feldspars mostly feature remarkably high K/Na compared to feldspars of comparable An from polymict ureilites. The EET 96001 feldspathic component was probably once part of a thin basaltic crust on a ureilite asteroid. The spinel included in one of the fassaites formed at remarkably high f0₂ (apparent oxidation state of iron: ～41 atom% Fe³⁺), suggesting that the parent magma possibly assimilated near‐surface water (however, the Fe³⁺ was not directly measured, and has conceivably been affected by terrestrial weathering; also, there is no assurance that this fassaite originated together with the typical feldspar). We speculate that the feldspathic component was mixed into the dense, Fe,S‐rich vein material, and very soon thereafter the Fe,S‐rich vein material was emplaced adjacent to the EET 96001 host ureilite, at an advanced stage in a chaotic catastrophic disruption and partial reassembly process that affected all ureilites. The high‐K nature of the EET 96001 feldspathic component, including the feldspathic glasses, suggests that fractional fusion may not have been as common during ureilite anatexis as has been inferred from recent studies of clast assemblages in polymict ureilites.     

The oxidation state of nanophase Fe particles in lunar soil: Implications for space weathering

We report measurements of the oxidation state of Fe nanoparticles within lunar soils that experienced varied degrees of space weathering. We measured >100 particles from immature, submature, and mature lunar samples using electron energy‐loss spectroscopy (EELS) coupled to an aberration‐corrected transmission electron microscope. The EELS measurements show that the nanoparticles are composed of a mixture of Fe⁰, Fe²⁺, and Fe³⁺ oxidation states, and exhibit a trend of increasing oxidation state with higher maturity. We hypothesize that the oxidation is driven by the diffusion of O atoms to the surface of the Fe nanoparticles from the oxygen‐rich matrix that surrounds them. The oxidation state of Fe in the nanoparticles has an effect on modeled reflectance properties of lunar soil. These results are relevant to remote sensing data for the Moon and to the remote determination of relative soil maturities for various regions of the lunar surface.     

The iron record of asteroidal processes in carbonaceous chondrites

The valence of iron has been used in terrestrial studies to trace the hydrolysis of primary silicate rocks. Here, we use a similar approach to characterize the secondary processes, namely thermal metamorphism and aqueous alteration, that have affected carbonaceous chondrites. X‐ray absorption near‐edge structure spectroscopy at the Fe‐K‐edge was performed on a series of 36 CM, 9 CR, 10 CV, and 2 CI chondrites. While previous studies have focused on the relative distribution of Fe⁰ with respect to oxidized iron (Fe_ox = Fe²⁺ + Fe³⁺) or the iron distribution in some specific phases (e.g., Urey–Craig diagram; Urey and Craig 1953), our measurements enable us to assess the fractions of iron in each of its three oxidation states: Fe⁰, Fe²⁺, and Fe³⁺. Among the four carbonaceous chondrites groups studied, a correlation between the iron oxidation index (IOI = [2(Fe²⁺) + 3(Fe³⁺)]/[Fe_TOT]) and the hydrogen content is observed. However, within the CM group, for which a progressive alteration sequence has been defined, a conversion of Fe³⁺ to Fe²⁺ is observed with increasing degree of aqueous alteration. This reduction of iron can be explained by an evolution in the mineralogy of the secondary phases. In the case of the few CM chondrites that experienced some thermal metamorphism, in addition to aqueous alteration, a redox memory of the aqueous alteration is present: a significant fraction of Fe³⁺ is present, together with Fe²⁺ and sometimes Fe⁰. From our data set, the CR chondrites show a wider range of IOI from 1.5 to 2.5. In all considered CR chondrites, the three oxidation states of iron coexist. Even in the least‐altered CR chondrites, the fraction of Fe³⁺ can be high (30% for MET 00426). This observation confirms that oxidized iron has been integrated during formation of fine‐grained amorphous material in the matrix (Le Guillou and Brearley 2014; Le Guillou et al. 2015; Hopp and Vollmer 2018). Last, the IOI of CV chondrites does not reflect the reduced/oxidized classification based on metal and magnetite proportions, but is strongly correlated with petrographic types. The valence of iron in CV chondrites therefore appears to be most closely related to thermal history, rather than aqueous alteration, even if these processes can occur together (Krot et al. 2004; Brearley and Krot 2013).     

“Sweating meteorites”—Water‐soluble salts and temperature variation in ordinary chondrites and soil from the hot desert of Oman

The common appearance of hygroscopic brine (“sweating”) on ordinary chondrites (OCs) from Oman during storage under room conditions initiated a study on the role of water‐soluble salts on the weathering of OCs. Analyses of leachates from OCs and soils, combined with petrography of alteration features and a 11‐month record of in situ meteorite and soil temperatures, are used to evaluate the role of salts in OC weathering. Main soluble ions in soils are Ca²⁺, SO₄^2?, HCO₃^?, Na⁺, and Cl^?, while OC leachates are dominated by Mg²⁺ (from meteoritic olivine), Ca²⁺ (from soil), Cl^? (from soil), SO₄^2? (from meteoritic troilite and soil), and iron (meteoritic). “Sweating meteorites” mainly contain Mg²⁺ and Cl^?. The median Na/Cl mass ratio of leachates changes from 0.65 in soils to 0.07 in meteorites, indicating the precipitation of a Na‐rich phase or loss of an efflorescent Na‐salt. The total concentrations of water‐soluble ions in bulk OCs ranges from 600 to 9000 μg g^?1 (median 2500 μg g^?1) as compared to 187–14140 μg g^?1 in soils (median 1148 μg g^?1). Soil salts dissolved by rain water are soaked up by meteorites by capillary forces. Daily heating (up to 66.3 °C) and cooling of the meteorites cause a pumping effect, resulting in a strong concentration of soluble ions in meteorites over time. The concentrations of water‐soluble ions in meteorites, which are complex mixtures of ions from the soil and from oxidation and hydrolysis of meteoritic material, depend on the degree of weathering and are highest at W3. Input of soil contaminants generally dominates over the ions mobilized from meteorites. Silicate hydrolysis preferentially affects olivine and is enhanced by sulfide oxidation, producing local acidic conditions as evidenced by jarosite. Plagioclase weathering is negligible. After completion of troilite oxidation, the rate of chemical weathering slows down with continuing Ca‐sulfate contamination.     

Short‐lived radioactivity in the early solar system: The Super‐AGB star hypothesis

Abstract– The composition of the most primitive solar system condensates, such as calcium‐aluminum‐rich inclusions (CAIs) and micron‐sized corundum grains, show that short‐lived radionuclides (SLR), e.g., ²⁶Al, were present in the early solar system. Their abundances require a local or stellar origin, which, however, is far from being understood. We present for the first time the abundances of several SLR up to ⁶⁰Fe predicted from stars with initial mass in the range approximately 7–11 M_⊙. These stars evolve through core H, He, and C burning. After core C burning they go through a “Super”‐asymptotic giant branch (Super‐AGB) phase, with the H and He shells activated alternately, episodic thermal pulses in the He shell, a very hot temperature at the base of the convective envelope (approximately 10⁸ K), and strong stellar winds driving the H‐rich envelope into the surrounding interstellar medium. The final remnants of the evolution of Super‐AGB stars are mostly O–Ne white dwarfs. Our Super‐AGB models produce ²⁶Al/²⁷Al yield ratios approximately 0.02–0.26. These models can account for the canonical value of the ²⁶Al/²⁷Al ratio using dilutions with the solar nebula of the order of 1 part of Super‐AGB mass per several 10² to several 10³ of solar nebula mass, resulting in associated changes in the O‐isotope composition in the range Δ¹⁷O from 3 to 20‰. This is in agreement with observations of the O isotopic ratios in primitive solar system condensates, which do not carry the signature of a stellar polluter. The radionuclides ⁴¹Ca and ⁶⁰Fe are produced by neutron captures in Super‐AGB stars and their meteoritic abundances are also matched by some of our models, depending on the nuclear and stellar physics uncertainties as well as the meteoritic experimental data. We also expect and are currently investigating Super‐AGB production of SLR heavier than iron, such as ¹⁰⁷Pd.     

Libyan Desert Glass area in western Egypt: Shocked quartz in bedrock points to a possible deeply eroded impact structure in the region

Libyan Desert Glass (LDG) is an enigmatic natural glass, about 28.5 million years old, which occurs on the floor of corridors between sand dunes of the southwestern corner of the Great Sand Sea in western Egypt, near the Libyan border. The glass occurs as centimeter‐ to decimeter‐sized, irregularly shaped, and strongly wind‐eroded pieces. The origin of the LDG has been the subject of much debate since its discovery, and a variety of exotic processes were suggested, including a hydrothermal sol‐gel process or a lunar volcanic source. However, evidence of an impact origin of these glasses included the presence of schlieren and partly or completely digested minerals, such as lechatelierite, baddeleyite (a high‐T breakdown product of zircon), and the presence of a meteoritic component in some of the glass samples. The source material of the glass remains an open question. Geochemical data indicate that neither the local sands nor sandstones from various sources in the region are good candidates to be the sole precursors of the LDG. No detailed studies of all local rocks exist, though. There are some chemical and isotopic similarity to rocks from the BP and Oasis impact structures in Libya, but no further evidence for a link between these structures and LDG was found so far. These complications and the lack of a crater structure in the area of the LDG strewn field have rendered an origin by airburst‐induced melting of surface rocks as a much‐discussed alternative. About 20 years ago, a few shocked quartz‐bearing breccias (float samples) were found in the LDG strewn field. To study this question further, several basement rock outcrops in the LDG area were sampled during three expeditions in the area. Here we report on the discovery of shock‐produced planar microdeformation features, namely planar fractures (PFs), planar deformation features (PDFs), and feather features (FFs), in quartz grains from bedrock samples. Our observations show that the investigated samples were shocked to moderate pressure, of at least 16 GPa. We interpret these observations to indicate that there was a physical impact event, not just an airburst, and that the crater has been almost completely eroded since its formation.     

The formation of Mg,Fe‐silicates by reactions between amorphous magnesiosilica smoke particles and metallic iron nanograins with implications for comet silicate origins

This thermal annealing experiment at 1000 K for up to 167 h used a physical mixture of vapor phase‐condensed magnesiosilica grains and metallic iron nanograins to test the hypothesis that a mixture of magnesiosilica grains and an Fe‐source would lead to the formation of ferromagnesiosilica grains. This exploratory study found that coagulation and thermal annealing of amorphous magnesiosilica and metallic grains yielded ferromagnesiosilica grains with the Fe/(Fe + Mg) ratios in interplanetary dust particles. Furthermore, decomposition of brucite present in the condensed magnesiosilica grains was the source for water and the cause of different iron oxidation states, and the formation of amorphous Fe³⁺‐ferrosilica, amorphous Fe³⁺‐Mg, Fe‐silicates, and magnesioferrite during thermal annealing. Fayalite and ferrosilite that formed from silica/FeO melts reacted with forsterite and enstatite to form Mg, Fe‐silicates. The presence of iron in different oxidation states in extraterrestrial materials almost certainly requires active asteroid‐like parent bodies. If so, the possible presence of trivalent Fe compounds in comet P/Halley suggests that Halley‐type comets are a mixture of preserved presolar and processed solar nebula dust. The results from this thermal annealing experiment further suggest that the Fe‐silicates detected in the impact‐induced ejecta from comet 9P/Temple 1 might be of secondary origin and related to the impact experiment or to processing in a regolith.     

Ultra‐reduced phases in Apollo 16 regolith: Combined field emission electron probe microanalysis and atom probe tomography of submicron Fe‐Si grains in Apollo 16 sample 61500

The lunar regolith contains a variety of chemically reduced phases of interest to planetary scientists and the most common, metallic iron, is generally ascribed to space weathering processes (Lucey et al. 2006 ). Reports of silicon metal and iron silicides, phases indicative of extremely reducing conditions, in lunar samples are rare (Anand et al. 2004 ; Spicuzza et al. 2011 ). Additional examples of Fe‐silicides have been identified in a survey of particles from Apollo 16 sample 61501,22. Herein is demonstrated the utility of low keV electron probe microanalysis (EPMA), using the Fe Ll X‐ray line, to analyze these submicron phases, and the necessity of accounting for carbon contamination. We document four Fe‐Si and Si⁰ minerals in lunar regolith return material. The new Fe‐Si samples have a composition close to (Fe,Ni)₃Si, whereas those associated with Si⁰ are close to FeSi₂ and Fe₃Si₇. Atom probe tomography of (Fe,Ni)₃Si shows trace levels of C (60 ppma and nanodomains enriched in C, Ni, P, Cr, and Sr). These reduced minerals require orders of magnitude lower oxygen fugacity and more reducing conditions than required to form Fe⁰. Documenting the similarities and differences in these samples is important to constrain their formation processes. These phases potentially formed at high temperatures resulting from a meteorite impact. Whether carbon played a role in achieving the lower oxygen fugacities—and there is evidence of nearby carbonaceous chondritic material—it remains to be proven that carbon was the necessary component for the unique existence of these Si⁰ and iron silicide minerals.     

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.     

Probing molecular and isotopic features of meteoritic insoluble organic matter by solid‐state nuclear magnetic resonance spectroscopy with sub‐milligram sample

We recorded one‐ and two‐dimensional solid‐state nuclear magnetic resonance spectra of meteoric insoluble organic matter with unprecedented sensitivity and resolution permitting us to reveal unambiguous spectroscopic fingerprints relevant to its molecular and isotopic features. Two‐dimensional ¹H‐¹H and ¹H‐¹³C correlation experiments have unveiled the spatial proximity between aliphatic and aromatic groups proving a highly branched character of a rigid macromolecular network composed of short aliphatic chains linking together small aromatic units. One‐dimensional ²H and two‐dimensional ¹H‐²H correlation spectroscopy delivered evidence of significant reduction in the deuterium enrichment of aromatic species relevant to interstellar processes, proto‐planetary disk chemistry, and to determining the origin of the meteoritic insoluble organic matter. The experimental approach developed in this work opens new perspectives for systematic and nondestructive analysis at the molecular level of meteoritic insoluble organic matter even with a very small amount of sample from some particularly rare chondrites.     

Differentiation processes in FeO‐rich asteroids revealed by the achondrite Lewis Cliff 88763

Olivine‐dominated (70–80 modal %) achondrite meteorite Lewis Cliff (LEW) 88763 originated from metamorphism and limited partial melting of a FeO‐rich parent body. The meteorite experienced some alteration on Earth, evident from subchondritic Re/Os, and redistribution of rhenium within the sample. LEW 88763 is texturally similar to winonaites, has a Δ¹⁷O value of ?1.19 ± 0.10‰, and low bulk‐rock Mg/(Mg+Fe) (0.39), similar to the FeO‐rich cumulate achondrite Northwest Africa (NWA) 6693. The similar bulk‐rock major‐, minor‐, and trace‐element abundances of LEW 88763, relative to some carbonaceous chondrites, including ratios of Pd/Os, Pt/Os, Ir/Os, and ¹⁸⁷Os/¹⁸⁸Os (0.1262), implies a FeO‐ and volatile‐rich precursor composition. Lack of fractionation of the rare earth elements, but a factor of approximately two lower highly siderophile element abundances in LEW 88763, compared with chondrites, implies limited loss of Fe‐Ni‐S melts during metamorphism and anatexis. These results support the generation of high Fe/Mg, sulfide, and/or metal‐rich partial melts from FeO‐rich parent bodies during partial melting. In detail, however, LEW 88763 cannot be a parent composition to any other meteorite sample, due to highly limited silicate melt loss (0 to <<5%). As such, LEW 88763 represents the least‐modified FeO‐rich achondrite source composition recognized to date and is distinct from all other meteorites. LEW 88763 should be reclassified as an anomalous achondrite that experienced limited Fe,Ni‐FeS melt loss. Lewis Cliff 88763, combined with a growing collection of FeO‐rich meteorites, such as brachinites, brachinite‐like achondrites, the Graves Nunataks (GRA) 06128/9 meteorites, NWA 6693, and Tafassasset, has important implications for understanding the initiation of planetary differentiation. Specifically, regardless of precursor compositions, partial melting and differentiation processes appear to be similar on asteroidal bodies spanning a range of initial oxidation states and volatile contents.     

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.