A nitrogen isotope study of bencubbinites

Abstract— ‐Nitrogen‐isotopic compositions of the bencubbinites—Bencubbin, Hammadah al Hamra (HH) 237, and Queen Alexandra Range (QUE) 94411—and in a petrographically similar chondrite Grosvenor Mountains (GRO) 95551 were measured by stepped‐combustion static mass spectrometry. Hammadah al Hamra 237 and QUE 94411 contain isotopically heavy N, but not as heavy as that in Bencubbin or Weatherford. Grosvenor Mountains 95551 contains isotopically near‐normal N and light N and, hence, it is not related to the bencubbinites, which is also indicated by its O‐isotopic composition. The N carriers in these meteorites were investigated using secondary ion mass spectrometry. In the bencubbinites, N is mostly located around sulfide in metal clasts and in impact‐melt areas. The N carriers in the former are taenite, carbide, or both; whereas those in the latter are molten metal, tiny graphitic carbon in metal, oxi‐nitride glass, or both. In the various N carriers, N is isotopically equilibrated, and therefore the carriers are not pristine presolar grains. Isotopically near‐normal N in GRO 95551 is located in graphite. The carrier of isotopically light N in GRO 95551 has not been found.     

NWA 1152 and Sahara 00182: New primitive carbonaceous chondrites with affinities to the CR and CV groups

Abstract— We have investigated the mineralogy, petrography, bulk chemistry, and light element isotope composition of the ungrouped chondrites North West Africa (NWA) 1152 and Sahara 00182. NWA 1152 contains predominantly type 1 porphyritic olivine (PO) and porphyritic olivinepyroxene (POP) chondrules. Chondrule silicates are magnesium‐rich (Fo_{98.8 ± 1.2}, n = 36; Fs_{2.3 ± 2.1} Wo_{1.2 ± 0.3}, n = 23). Matrix comprises ?40 vol% of the sample and is composed of a micron sized silicate groundmass with larger silicate, sulfide, magnetite, and Fe‐Ni metal (Ni ?50 wt%) grains. Phyllosilicates were not observed in the matrix. Refractory inclusions are rare (0.3 vol%) and are spinel pyroxene aggregates or amoeboid olivine aggregates; melilite is absent from the refractory inclusions. Sahara 00182 contains predominantly type 1 PO chondrules, POP chondrules are less common. Most chondrules contain blebs of, and are often rimmed with, Fe‐Ni metal and sulfide. Chondrule phenocrysts are magnesium‐rich (Fo_{92.2 ± 0.6}, n = 129; Fs_{4.4 ± 1.8} Wo_{1.3 ± 1.1}, n = 16). Matrix comprises ?30 vol% of the meteorite and is predominantly sub‐micron silicates, with rare larger silicate gains. Matrix Fe‐Ni metal (mean Ni = 5.8 wt%) and sulfide grains are up to mm scale. No phyllosilicates were observed in the matrix. Refractory inclusions are rare (1.1 vol%) and melilite is absent. The oxygen isotope composition of NWA 1152 falls within the range of the CV chondrites with δ¹⁷O = ?3.43%0 δ¹⁸O = 0.70%0 and is similar to Sahara 00182, δ¹⁷O = ?3.89%0, δ¹⁸O = ?0.19%0 (Grossman and Zipfel 2001). Based on mineralogical and petrographic characteristics, we suggest NWA 1152 and Sahara 00182 show many similarities with the CR chondrites, however, oxygen isotopes suggest affinity with the CVs. Thus, neither sample can be assigned to any of the currently known carbonaceous chondrite groups based on traditionally recognized characteristics. Both samples demonstrate the complexity of inter‐ and intra‐group relationships of the carbonaceous chondrites. Whatever their classification, N WA 1152 and Sahara 00182 represent a source of relatively pristine solar system material.     

A NanoSIMS and Auger Nanoprobe investigation of an isotopically primitive interplanetary dust particle from the 55P/Tempel‐Tuttle targeted stratospheric dust collector

Abstract– An IDP nicknamed Andric, from a stratospheric dust collector targeted to collect dust from comet 55P/Tempel‐Tuttle, contains five distinct presolar silicate and/or oxide grains in 14 ultramicrotome slices analyzed, for an estimated abundance of approximately 700 ppm in this IDP. Three of the grains are ¹⁷O‐enriched and probably formed in low‐mass red giant or asymptotic giant branch (AGB) stars; the other two grains exhibit ¹⁸O enrichments and may have a supernova origin. Carbon and N isotopic analyses show that Andric also exhibits significant variations in its N isotopic composition, with numerous discrete ¹⁵N‐rich hotspots and more diffuse regions that are also isotopically anomalous. Three ¹⁵N‐rich hotspots also have statistically significant ¹³C enrichments. Auger elemental analysis shows that these isotopically anomalous areas consist largely of carbonaceous matter and that the anomalies may be hosted by a variety of components. In addition, there is evidence for dilution of the isotopically heavy components with an isotopically normal endmember; this may have occurred either as a result of extraterrestrial alteration or during atmospheric entry. Isotopically primitive IDPs such as Andric share many characteristics with primitive meteorites such as the CR chondrites, which also contain isotopically anomalous carbonaceous matter and abundant presolar silicate and oxide grains. Although comets are one likely source for the origin of primitive IDPs, the presence of similar characteristics in meteorites thought to come from the asteroid belt suggests that other origins are also possible. Indeed the distinction between cometary and asteroidal sources is somewhat blurred by recent observations of icy comet‐like planetesimals in the outer asteroid belt.     

Silicon and iron isotopes in components of enstatite chondrites: Implications for metal–silicate–sulfide fractionation in the solar nebula

Silicon and iron isotope compositions of different physically separated components of enstatite chondrites (EC) were determined in this study to understand the role of nebular and planetary scale events in fractionating Si and Fe isotopes of the terrestrial planet-forming region. We found that the metal–sulfide nodules of EC are strongly enriched in light Si isotopes (δ³⁰Si ≥ −5.61 ± 0.12‰, 2SD), whereas the δ³⁰Si values of angular metal grains, magnetic, slightly magnetic, and non-magnetic fractions become progressively heavier, correlating with their Mg# (Mg/(Mg+Fe)). White mineral phases, composed primarily of SiO₂ polymorphs, display the heaviest δ³⁰Si of up to +0.23 ± 0.10‰. The data indicate a key role of metal–silicate partitioning on the Si isotope composition of EC. The overall lighter δ³⁰Si of bulk EC compared to other planetary materials can be explained by the enrichment of light Si isotopes in EC metals along with the loss of isotopically heavier forsterite-rich silicates from the EC-forming region. In contrast to the large Si isotope heterogeneity, the average Fe isotope composition (δ⁵⁶Fe) of EC components was found to vary from −0.30 ± 0.08‰ to +0.20 ± 0.04‰. A positive correlation between δ⁵⁶Fe and Ni/S in the components suggests that the metals are enriched in heavy Fe isotopes whereas sulfides are the principal hosts of light Fe isotopes in the non-magnetic fractions of EC. Our combined Si and Fe isotope data in different EC components reflect an inverse correlation between δ³⁰Si and δ⁵⁶Fe, which illustrates that partitioning of Si and Fe among metal, silicate, and sulfidic phases has significantly fractionated Si and Fe isotopes under reduced conditions. Such isotope partitioning must have occurred before the diverse components were mixed to form the EC parent body. Evaluation of diffusion coefficients of Si and Fe in the metal and non-metallic phases suggests that the Si isotope compositions of the silicate fractions of EC largely preserve information of their nebular processing. On the other hand, the Fe isotopes might have undergone partial or complete re-equilibration during parent body metamorphism. The relatively uniform δ⁵⁶Fe among different types of bulk chondrites and the Earth, despite Fe isotope differences among their components, demonstrates that the chondrite parent bodies were not formed by random mixing of chondritic components from different locations in the disk. Instead, the chondrite components mostly originated in the same nebular reservoir and Si and Fe isotopes were fractionated either due to gas–solid interactions and associated changes in physicochemical environment of the nebular reservoir and/or during parent body processing. The heavier Si isotope composition of the bulk silicate Earth may require accretion of chondritic and/or isotopically heavier EC silicates along with cumulation of refractory forsterite-rich heavier silicates lost from the EC-forming region to form the silicate reservoir of the Earth.     

The Isheyevo meteorite: Mineralogy,petrology, bulk chemistry,oxygen, nitrogen,carbon isotopic compositions,and 40Ar‐39Ar ages

Abstract— Isheyevo is a metal‐rich carbonaceous chondrite that contains several lithologies with different abundances of Fe,Ni metal (7–90 vol%). The metal‐rich lithologies with 50–60 vol% of Fe,Ni metal are dominant. The metal‐rich and metal‐poor lithologies are most similar to the CB_b and CH carbonaceous chondrites, respectively, providing a potential link between these chondrite groups. All lithologies experienced shock metamorphism of shock stage S4. All consist of similar components—Fe,Ni metal, chondrules, refractory inclusions (Ca, Al‐rich inclusions [CAIs] and amoeboid olivine aggregates [AOAs]), and heavily hydrated lithic clasts—but show differences in their modal abundances, chondrule sizes, and proportions of porphyritic versus non‐porphyritic chondrules. Bulk chemical and oxygen isotopic compositions are in the range of CH and CB chondrites. Bulk nitrogen isotopic composition is highly enriched in ¹⁵N (δ¹⁵N = 1122‰). The magnetic fraction is very similar to the bulk sample in terms of both nitrogen release pattern and isotopic profile; the non‐magnetic fraction contains significantly less heavy N. Carbon released at high temperatures shows a relatively heavy isotope signature. Similarly to CB_b chondrites, ～20% of Fe,Ni‐metal grains in Isheyevo are chemically zoned. Similarly to CH chondrites, some metal grains are Ni‐rich (>20 wt% Ni). In contrast to CB_b and CH chondrites, most metal grains are thermally decomposed into Ni‐rich and Ni‐poor phases. Similar to CH chondrites, chondrules have porphyritic and non‐porphyritic textures and ferromagnesian (type I and II), silica‐rich, and aluminum‐rich bulk compositions. Some of the layered ferromagnesian chondrules are surrounded by ferrous olivine or phyllosilicate rims. Phyllosilicates in chondrule rims are compositionally distinct from those in the hydrated lithic clasts. Similarly to CH chondrites, CAIs are dominated by the hibonite‐, grossite‐, and melilite‐rich types; AOAs are very rare. We infer that Isheyevo is a complex mixture of materials formed by different processes and under different physico‐chemical conditions. Chondrules and refractory inclusions of two populations, metal grains, and heavily hydrated clasts accreted together into the Isheyevo parent asteroid in a region of the protoplanetary disk depleted in fine‐grained dust. Such a scenario is consistent with the presence of solar wind—implanted noble gases in Isheyevo and with its comparatively old K‐Ar age. We cannot exclude that the K‐Ar system was affected by a later collisional event. The cosmic‐ray exposure (CRE) age of Isheyevo determined by cosmogenic ³⁸Ar is ～34 Ma, similar to that of the Bencubbin (CB_a) meteorite.     

Fractionated sulfur isotopes in sulfides of the Kaidun meteorite

Abstract— The Kaidun meteorite contains carbonaceous chondrite (CM1) clasts that have been highly altered by reactions with hydrothermal fluids. Pyrrhotite in these clasts occurs as unusual needles wrapped by sheaths of phyllosilicate, and pentlandite forms veins that crosscut aggregates of phyllosilicate and garnet but not pyrrhotite. The isotopic compositions of S (δ³⁴S_CDT) in individual sulfide grains, measured by ion micro-probe, are fractionated compared to troilite in ordinary chondrites. The S in Kaidun sulfides is isotopically light (as much as ?4.2% for pyrrhotite and ?5.7%0 for pentlandite), unlike sulfides in other carbonaceous chondrites, which are enriched in ³⁴S. The unusual S-isotopic composition of these texturally unique sulfides supports the hypothesis that Kaidun CM1 clasts were pervasively altered under extreme thermal conditions, possibly by fluids that had lost isotopically heavy SO₂.     

Oxygen isotope and chemical compositions of magnetite and olivine in the anomalous CK3 Watson 002 and ungrouped Asuka‐881595 carbonaceous chondrites: Effects of parent body metamorphism

We report in situ O isotope and chemical compositions of magnetite and olivine in chondrules of the carbonaceous chondrites Watson‐002 (anomalous CK3) and Asuka (A)‐881595 (ungrouped C3). Magnetite in Watson‐002 occurs as inclusion‐free subhedral grains and rounded inclusion‐bearing porous grains replacing Fe,Ni‐metal. In A‐881595, magnetite is almost entirely inclusion‐free and coexists with Ni‐rich sulfide and less abundant Ni‐poor metal. Oxygen isotope compositions of chondrule olivine in both meteorites plot along carbonaceous chondrite anhydrous mineral (CCAM) line with a slope of approximately 1 and show a range of Δ¹⁷O values (from approximately ?3 to ?6‰). One chondrule from each sample was found to contain O isotopically heterogeneous olivine, probably relict grains. Oxygen isotope compositions of magnetite in A‐881595 plot along a mass‐dependent fractionation line with a slope of 0.5 and show a range of Δ¹⁷O values from ?2.4‰ to ?1.1‰. Oxygen isotope compositions of magnetite in Watson‐002 cluster near the CCAM line and a Δ¹⁷O value of ?4.0‰ to ?2.9‰. These observations indicate that magnetite and chondrule olivine are in O isotope disequilibrium, and, therefore, not cogenetic. We infer that magnetite in CK chondrites formed by the oxidation of pre‐existing metal grains by an aqueous fluid during parent body alteration, in agreement with previous studies. The differences in Δ¹⁷O values of magnetite between Watson‐002 and A‐881595 can be attributed to their different thermal histories: the former experienced a higher degree of thermal metamorphism that led to the O isotope exchange between magnetite and adjacent silicates.     

Mineralogy of fine‐grained material in the Krymka (LL3.1) chondrite

Abstract— Two dark lithic fragments and matrix of the Krymka LL3.1 chondrite were mineralogically and chemically studied in detail. These objects are characterised by the following chemical and mineralogical characteristics, which distinguish them from the host chondrite Krymka: (1) bulk chemical analyses revealed low totals (systematically lower than 94 wt%) due to high porosity; (2) enrichment in FeO and depletion in S, MgO and SiO₂ due to a high abundance of Fe‐rich silicates and low sulfide abundance; (3) fine‐grained, almost chondrule‐free texture with predominance of a porous, cryptocrystalline groundmass and fine grains; (4) occurrence of a small amount of once‐molten material (microchondrules) enclosed in fine‐grained materials; (5) occurrence of accretionary features, especially unique accretionary spherules; (6) high abundance of small calcium‐ aluminium‐rich inclusions (CAIs) in one of the fine‐grained fragments. It is suggested that the abundance of CAIs in this fragment is one of the highest ever found in an ordinary chondrite. Accretionary, fine‐grained spherules within one of the fragments bear fundamental information about the initial stages of accretion as well as on the evolution of the clast, its incorporation, and history within the bulk rock of Krymka. The differences in porosity, bulk composition, and mineralogy of cores and rims of the fine‐grained spherulitic objects allow us to speculate on the following processes: (1) Low velocity accretion of tiny silicate grains onto the surface of coarse metal or silicate grains in a dusty region of the nebula is the beginning of the formation of accretionary, porous (fluffy) silicate spherules. (2) Within a dusty environment with decreasing silicate/(metal + sulfide) ratio the porous spherules collected abundant metal and sulfide particles together with silicate dust, which formed an accretionary rim. Variations of the silicate/(sulfide + metal) ratio in the dusty nebular environment result in the formation of multi‐layered rims on the surface of the silicate‐rich spherules. (3) Soft accretion and lithification of rimmed, fluffy spherules, fine‐grained, silicate‐rich dust, metal‐sulfide particles, CAIs, silicate‐rich microchondrules, and coarse silicate grains and fragments followed. (4) After low‐temperature processing of the primary, accretionary rock collisional fragmentation occurred, the fragments were subsequently coated by fine‐grained material, which was highly oxidized and depleted in sulfides. (5) In a final stage this accretionary “dusty” rock was incorporated as a fragment within the Krymka host.     

Sulfide–oxide assemblages in Acfer 094—Clues to nebular metal–gas interactions

The ungrouped carbonaceous chondrite Acfer 094 is among the least altered samples of the early solar system. We have studied concentric sulfide–oxide aggregates from this meteorite by transmission electron microscopy (TEM) and nanoscale secondary ion mass spectrometry (NanoSIMS). The main minerals present are magnetite, pentlandite, and pyrrhotite/troilite. The outer parts of the aggregates include μm-sized olivine and pyroxenes with variable Mg/Fe ratios. One aggregate contains taenite (56.7 wt% Ni) within its central part that is surrounded by pentlandite and magnetite. We conclude that both phases have formed by oxidation and sulfidization of metal and, based on the metal and sulfide Fe/Ni ratio, a (sulfide)-formation temperature of 400–550 °C can be constrained. This temperature is higher than any temperature that could be expected to have occurred on the Acfer 094 parent body, and also textural evidence indicates that the aggregates formed before parent-body accretion. We therefore conclude that the formation of the sulfide–oxide aggregates occurred most likely in the solar nebular at highly variable H₂O and H₂S fugacities. Oxygen-isotopic compositions of magnetite within these assemblages show that they are indistinguishable from the meteorite's matrix (δ¹⁷O_SMOW ≈ 4 ± 8‰, δ¹⁸O_SMOW ≈ 10 ± 6‰, and ∆¹⁷O_SMOW ≈ −1 ± 5‰). An enrichment of ^17,18O relative to chondrules of Acfer 094 suggests a link between the formation of the sulfide–oxide aggregates and the preaccretionary processing of matrix grains in a volatile-enriched nebular environment.     

The origin of chondritic macromolecular organic matter: A carbon and nitrogen isotope study

Abstract— The N and C abundances and isotopic compositions of acid-insoluble carbonaceous material in thirteen primitive chondrites (five unequilibrated ordinary chondrites, three CM chondrites, three enstatite chondrites, a CI chondrite and a CR chondrite) have been measured by stepped combustion. While the range of C isotopic compositions observed is only ～δ¹³C = 30%, the N isotopes range from δ¹⁵N ' -40 to 260%. After correction for metamorphism, presolar nanodiamonds appear to have made up a fairly constant 3–4 wt% of the insoluble C in all the chondrites studied. The apparently similar initial presolar nanodiamond to organic C ratios, and the correlations of elemental and isotopic compositions with metamorphic indicators in the ordinary and enstatite chondrites, suggest that the chondrites all accreted similar organic material. This original material probably most closely resembles that now found in Renazzo and Semarkona. These two meteorites have almost M-shaped N isotope release profiles that can be explained most simply by the superposition of two components, one with a composition between δ¹⁵N = -20 and -40% and a narrow combustion interval, the other having a broader release profile and a composition of δ¹⁵N ～ 260%. Although isotopically more subdued, the CI and the three CM chondrites all appear to show vestiges of this M-shaped profile. How and where the components in the acid-insoluble organics formed remains poorly constrained. The small variation in nanodiamond to organic C ratio between the chondrite groups limits the local synthesis of organic matter in the various chondrite formation regions to at most 30%. The most ¹⁵N-rich material probably formed in the interstellar medium, and the fraction of organic N in Renazzo in this material ranges from 40 to 70%. The isotopically light component may have formed in the solar system, but the limited range in nanodiamond to total organic C ratios in the chondrite groups is consistent with most of the organic material being presolar.     

Ferrous silicate spherules with euhedral iron‐nickel metal grains from CH carbonaceous chondrites: Evidence for supercooling and condensation under oxidizing conditions

Abstract— The CH carbonaceous chondrites contain a population of ferrous (Fe/(Fe + Mg) ? 0.1‐0.4) silicate spherules (chondrules), about 15–30 μm in apparent diameter, composed of cryptocrystalline olivinepyroxene normative material, ±SiO₂‐rich glass, and rounded‐to‐euhedral Fe, Ni metal grains. The silicate portions of the spherules are highly depleted in refractory lithophile elements (CaO, Al₂O₃, and TiO₂ <0.04 wt%) and enriched in FeO, MnO, Cr₂O₃, and Na₂O relative to the dominant, volatile‐poor, magnesian chondrules from CH chondrites. The Fe/(Fe + Mg) ratio in the silicate portions of the spherules is positively correlated with Fe concentration in metal grains, which suggests that this correlation is not due to oxidation, reduction, or both of iron (FeO_sil ? Fe_met) during melting of metal‐silicate solid precursors. Rather, we suggest that this is a condensation signature of the precursors formed under oxidizing conditions. Each metal grain is compositionally uniform, but there are significant intergrain compositional variations: about 8–18 wt% Ni, <0.09 wt% Cr, and a sub‐solar Co/Ni ratio. The precursor materials of these spherules were thus characterized by extreme elemental fractionations, which have not been observed in chondritic materials before. Particularly striking is the fractionation of Ni and Co in the rounded‐to‐euhedral metal grains, which has resulted in a Co/Ni ratio significantly below solar. The liquidus temperatures of the euhedral Fe, Ni metal grains are lower than those of the coexisting ferrous silicates, and we infer that the former crystallized in supercooled silicate melts. The metal grains are compositionally metastable; they are not decomposed into taenite and kamacite, which suggests fast postcrystallization cooling at temperatures below 970 K and lack of subsequent prolonged thermal metamorphism at temperatures above 400–500 K.     

The Fountain Hills impact‐modified CB chondrite and thermal history of the CB asteroid

Abstract— Fountain Hills is a metal‐rich chondrite with mineral and whole chondrite oxygen isotope compositions that suggest it is a CB chondrite. However, its petrologic characteristics suggest that it has been modified by shock and recrystallization to a greater degree than other CB chondrites. It differs texturally from the CB chondrites in that its metal is interstitial to the silicate and does not occur as discrete clasts as in the other CB chondrites. Portions of Fountain Hills appear to be recrystallized and it contains large (mm‐size) olivine rimmed by pyroxene. A characteristic of the CB chondrites is the presence of small sulfide blebs in large metal clasts and anomalously heavy (¹⁵N‐enriched) nitrogen often associated with metal surrounding the sulfide blebs, but Fountain Hills lacks sulfide and its nitrogen is relatively light. The differences between Fountain Hills and the other CB chondrites can be attributed to a secondary process, most likely impact‐melting and recrystallization, that overprinted its primary features and it is inferred that Fountain Hills is an impact‐modified CB chondrite.     

Interstellar graphite in meteorites: Isotopic compositions and structural properties of single graphite grains from Murchison

Abstract— One hundred forty-three carbon grains, ranging in size from 2 to 8 μm, from two chemical and physical separates from the Murchison CM2 chondrite, were analyzed by ion microprobe mass spectrometry for their C- and N-isotopic compositions. Both separates are enriched in the exotic noble gas component Ne-E(L). Ninety grains were also analyzed for their H and O contents and 118, for Si. Thirteen grains were analyzed by micro-sampling laser Raman spectroscopy. Round grains have large C-isotopic anomalies with ¹²C/¹³C ratios ranging from 7 to 4500 (terrestrial ratio = 89). Nitrogen in these grains is also anomalous but shows much smaller deviations from the terrestrial composition, ¹⁴N/¹⁵N ratios ranging from 193 to 680 (terrestrial ratio = 272). Spherulitic aggregates and non-round compact grains have normal C-isotopic ratios but ¹⁵N excesses (up to 35%). Raman spectra of the analyzed grains indicate varying degrees of crystalline disorder of graphite with estimated in-plane crystallite dimensions varying from 18 Å (highly disordered, similar to terrestrial kerogen) to ～750 Å (well-crystallized graphite). Element contents of H, O, and Si are correlated with one another, and H and O are probably present in the form of organic molecules. On the basis of morphology, the round grains fall into two groups: grains with smooth, shell-like surfaces (“onions”) and grains that appear to be dense aggregates of small scales (“cauliflowers”). “Onions” tend to have lower trace element contents, isotopically light C (¹²C/¹³C > 89) and a high degree of crystalline order, whereas “cauliflowers” have a larger spread in trace element contents and C-isotopic ratios (they range from isotopically light to heavy) but tend to have a low degree of crystalline order. However, these differences exist only on average, and no clear distinction can be made for individual grains. A few limited conclusions can be drawn about the astrophysical origin of the carbon grains of this study. The ¹⁵N excesses in spherulitic aggregates and non-round grains can be explained as the result of ion-molecule reactions in molecular clouds. The round grains, on the other hand, must have formed in stellar atmospheres (circumstellar grains). Grains with isotopically light C must have formed in stellar environments characterized by He-burning, either in the atmosphere of Wolf-Rayet stars during the WC phase or in the He-burning, ¹²C-rich zone of a massive star, ejected by a supernova explosion. Isotopically heavy C is produced by H-burning in the CNO cycle. Possible sources for grains with heavy C are carbon stars (AGB stars during the thermally pulsing phase) or novae, but the detailed distribution of ¹²C/¹³C ratios agree neither with the distribution observed in carbon stars nor with theoretical predictions for these two types of stellar sources.     

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.     

Opaque assemblages in CR2 Graves Nunataks (GRA) 06100 as indicators of shock‐driven hydrothermal alteration in the CR chondrite parent body

We have studied the petrologic characteristics of sulfide‐metal lodes, polymineralic Fe‐Ni nodules, and opaque assemblages in the CR2 chondrite Graves Nunataks (GRA) 06100, one of the most altered CR chondrites. Unlike low petrologic type CR chondrites, alteration of metal appears to have played a central role in the formation of secondary minerals in GRA 06100. Differences in the mineralogy and chemical compositions of materials in GRA 06100 suggest that it experienced higher temperatures than other CR2 chondrites. Mineralogic features indicative of high temperature include: (1) exsolution of Ni‐poor and Ni‐rich metal from nebular kamacite; (2) formation of sulfides, oxides, and phosphates; (3) changes in the Co/Ni ratios; and (4) carbidization of Fe‐Ni metal. The conspicuous absence of pentlandite may indicate that peak temperatures exceeded 600 °C. Opaques appear to have been affected by the action of aqueous fluids that resulted in the formation of abundant oxides, Fe‐rich carbonates, including endmember ankerite, and the sulfide‐silicate‐phosphate scorzalite. We suggest that these materials formed via impact‐driven metamorphism. Mineralogic features indicative of impact metamorphism include (1) the presence of sulfide‐metal lodes; (2) the abundance of polymineralic opaque assemblages with mosaic‐like textures; and (3) the presence of suessite. Initial shock metamorphism probably resulted in replacement of nebular Fe‐Ni metal in chondrules and in matrix by Ni‐rich, Co‐rich Fe metal, Al‐Ti‐Cr‐rich alloys, and Fe sulfides, while subsequent hydrothermal alteration produced accessory oxides, phosphates, and Fe carbonates. An extensive network of sulfide‐metal veins permitted effective exchange of siderophile elements from pre‐existing metal nodules with adjacent chondrules and matrix, resulting in unusually high Fe contents in these objects.     

Re‐examining the role of chondrules in producing the elemental fractionations in chondrites

Abstract— The matrices of all primitive chondrites contain presolar materials (circumstellar grains and interstellar organics) in roughly CI abundances, suggesting that all chondrites accreted matrix that is dominated by a CI‐like component. The matrix‐normalized abundances of the more volatile elements (condensation temperatures <750–800 K) in carbonaceous and ordinary chondrites are also at or slightly above CI levels. The modest excesses may be due to low levels of these elements in chondrules and associated metal. Subtraction of a CI‐like matrix component from a bulk ordinary chondrite composition closely matches the average composition of chondrules determined by instrumental neutron activation analysis (INAA) if some Fe‐metal is added to the chondrule composition. Measured matrix compositions are not CI‐like. Sampling bias and secondary redistribution of elements may have played a role, but the best explanation is that ?10–30% of refractory‐rich, volatile depleted material was added to matrix. If most of the more volatile elements are in a CI‐dominated matrix, the major and volatile element fractionations must be largely carried by chondrules. There is both direct and indirect evidence for evaporation during chondrule formation. Type IIA and type B chondrules could have formed from a mixture of CI material and material evaporated from type IA chondrules. The Mg‐Si‐Fe fractionations in the ordinary chondrites can be reproduced with the loss of type IA chondrule material and associated metal. The loss of evaporated material from the chondrules could explain the volatile element fractionations. Mechanisms for how these fractionations occurred are necessarily speculative, but two possibilities are briefly explored.     

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

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

A cornucopia of presolar and early solar system materials at the micrometer size range in primitive chondrite matrix

Abstract— We have used a variety of complementary microanalytical techniques to constrain the mineralogy, trace‐element distributions, and oxygen‐isotopic compositions in a 50 × 50 μm area of Acfer 094 matrix. The results reveal the exceptional mineralogical and compositional heterogeneity of this material at the sub‐μm level. We observe μm‐scale and sub‐μm grains with elemental associations suggesting feldspar, metal with widely varying Ni contents, and a Cr‐Fe alloy (in addition to forsterite, pyroxene, sulfide, ferrihydrite, and amorphous groundmass previously described). A new class of μm‐scale CAI (μCAI) is also observed, which show sub‐μm compositional zoning, and a range of oxygen isotopic compositions. Unlike the larger CAIs in Acfer 094, which are uniformly ¹⁶O‐enriched, two of the three μCAIs we analyzed are isotopically normal. We also observed a Li‐rich hotspot that detailed analysis by ToF‐SIMS suggests may be a LiCr‐oxide grain. Within the resolution of the NanoSIMS, this grain has isotopically normal Li. Finally, in our 50 × 50 μm area, we positively identified a presolar grain that is the most ¹⁸O‐rich silicate found so far in meteorites. The grain may originate from an asymptotic giant branch (AGB) star, or more likely, a supernova. In line with previous TEM studies (Greshake 1997), we find no evidence for clastic material (e.g., fragmental chondrules) in the matrix of Acfer 094: although the matrix is volatile‐depleted, this depletion does not appear to result from dilution of a primordial starting material with (depleted) chondrule fragments. Assuming that matrix experienced the depletion event, our data on the detailed mineralogy of Acfer 094 are currently equivocal in constraining the nature of that event. We observe carrier phases for several elements consistent with conditions approaching equilibrium condensation; however, the presence of an amorphous groundmass is suggestive of more rapid cooling.     

Petrography,stable isotope compositions,microRaman spectroscopy,and presolar components of Roberts Massif 04133: A reduced CV3 carbonaceous chondrite

Here, we report the mineralogy, petrography, C‐N‐O‐stable isotope compositions, degree of disorder of organic matter, and abundances of presolar components of the chondrite Roberts Massif (RBT) 04133 using a coordinated, multitechnique approach. The results of this study are inconsistent with its initial classification as a Renazzo‐like carbonaceous chondrite, and strongly support RBT 04133 being a brecciated, reduced petrologic type >3.3 Vigarano‐like carbonaceous (CV) chondrite. RBT 04133 shows no evidence for aqueous alteration. However, it is mildly thermally altered (up to approximately 440 °C); which is apparent in its whole‐rock C and N isotopic compositions, the degree of disorder of C in insoluble organic matter, low presolar grain abundances, minor element compositions of Fe,Ni metal, chromite compositions and morphologies, and the presence of unequilibrated silicates. Sulfides within type I chondrules from RBT 04133 appear to be pre‐accretionary (i.e., did not form via aqueous alteration), providing further evidence that some sulfide minerals formed prior to accretion of the CV chondrite parent body. The thin section studied contains two reduced CV3 lithologies, one of which appears to be more thermally metamorphosed, indicating that RBT 04133, like several other CV chondrites, is a breccia and thus experienced impact processing. Linear foliation of chondrules was not observed implying that RBT 04133 did not experience high velocity impacts that could lead to extensive thermal metamorphism. Presolar silicates are still present in RBT 04133, although presolar SiC grain abundances are very low, indicating that the progressive destruction or modification of presolar SiC grains begins before presolar silicate grains are completely unidentifiable.     

Structure,composition, and location of organic matter in the enstatite chondrite Sahara 97096 (EH3)

Abstract– The insoluble organic matter (IOM) of an unequilibrated enstatite chondrite Sahara (SAH) 97096 has been investigated using a battery of analytical techniques. As the enstatite chondrites are thought to have formed in a reduced environment at higher temperatures than carbonaceous chondrites, they constitute an interesting comparative material to test the heterogeneities of the IOM in the solar system and to constrain the processes that could affect IOM during solar system evolution. The SAH 97096 IOM is found in situ: as submicrometer grains in the network of fine‐grained matrix occurring mostly around chondrules and as inclusions in metallic nodules, where the carbonaceous matter appears to be more graphitized. IOM in these two settings has very similar δ¹⁵N and δ¹³C; this supports the idea that graphitized inclusions in metal could be formed by metal catalytic graphitization of matrix IOM. A detailed comparison between the IOM extracted from a fresh part and a terrestrially weathered part of SAH 97096 shows the similarity between both IOM samples in spite of the high degree of mineral alteration in the latter. The isolated IOM exhibits a heterogeneous polyaromatic macromolecular structure, sometimes highly graphitized, without any detectable free radicals and deuterium‐heterogeneity and having mean H‐ and N‐isotopic compositions in the range of values observed for carbonaceous chondrites. It contains some submicrometer‐sized areas highly enriched in ¹⁵N (δ¹⁵N up to 1600‰). These observations reinforce the idea that the IOM found in carbonaceous chondrites is a common component widespread in the solar system. Most of the features of SAH 97096 IOM could be explained by the thermal modification of this main component.