Origins of meteoritic nanodiamonds investigated by coordinated atom‐probe tomography and transmission electron microscopy studies

To constrain the origins of meteoritic nanodiamonds, the abundance ratios of stable C isotopes in acid residues from the carbonaceous chondritic meteorite Allende CV3 were measured using coordinated atom‐probe tomography (APT) and transmission electron microscopy (TEM). We combined our data with previously published APT data. A statistical analysis of this combined data set suggests an upper bound of 1 in 10² on the subpopulation that could have a large isotopic enrichment in ¹³C relative to ¹²C, consistent with the possible detection by secondary ion mass spectrometry of a similar enrichment in a 1 in 10⁵ fraction, abundant enough to account for the Xe‐HL anomalous isotopic component carried by the acid residues. Supernovae are believed to be the source of Xe‐HL, leading to the mystery of why all other supernova minerals do not carry Xe‐HL. The lack of Xe‐HL in low‐density disordered supernova graphite suggests that the isotopically anomalous component is the nanodiamonds, but the disordered C in the residue is not ruled out. We discuss possible origins of the disordered C and implications of our results for proposed formation scenarios for nanodiamonds. At least 99% of the meteoritic acid residue exhibits no unambiguous evidence of presolar formation, although production with solar isotope ratios in asymptotic giant branch stars is not ruled out. Comparison of TEM and APT results indicates that a minority of the APT reconstructions may preferentially sample disordered C rather than nanodiamonds. If this is the case, a presolar origin for a larger fraction of the nanodiamonds remains possible.     

Search for extinct aluminum‐26 and titanium‐44 in nanodiamonds from the Allende CV3 and Murchison CM2 meteorites

Abstract– We report Mg‐Al and Ca‐Ti isotopic data for meteoritic nanodiamonds separated from the Allende CV3 and Murchison CM2 meteorites. The goal of this study was to search for excesses in ²⁶Mg and ⁴⁴Ca, which can be attributed to the in situ decay of radioactive and now extinct ²⁶Al and ⁴⁴Ti, respectively. Previous work on presolar SiC and graphite had shown that ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios in presolar grains can be used to discriminate between different types of stellar sources. Aluminum and Ti concentrations are low in the meteoritic nanodiamonds of this study. Murchison nanodiamonds have higher Al and Ti concentrations than the Allende nanodiamonds. This can be attributed to contamination and the presence of presolar SiC in the Murchison nanodiamond samples. ²⁶Mg/²⁴Mg and ⁴⁴Ca/⁴⁰Ca ratios are close to normal in Allende nanodiamonds with upper limits on the initial ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios of approximately 1 × 10^?3. These ratios are factors of 10–1000 and, respectively, 1–1000 lower than those of presolar SiC and graphite grains from supernovae. The ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti data for nanodiamonds are compatible with an asymptotic giant branch star or solar system origin, but not with a supernova origin of a major fraction of meteoritic nanodiamonds. The latter possibility cannot be excluded, though, as the diamond separates may contain significant amounts of contaminating Al and Ti, which would lower the inferred ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios considerably.     

Noble gases in presolar diamonds III: Implications of ion implantation experiments with synthetic nanodiamonds

Abstract— A series of experiments carried out by Koscheev et al. (1998, 2001, 2004, 2005) showed that the bimodal release of heavy noble gases from meteoritic nanodiamonds can be reproduced by a single implanted component. This paper investigates the implications of this result for interpreting the noble gas compositions of meteoritic nanodiamonds and for their origin and history. If the bimodal release exhibited by meteorite diamonds reflects release of the P3 noble gas component, then the composition inferred for the pure Xe‐HL end member changes slightly, the excesses of heavy krypton isotopes that define Kr‐H become less extreme, evidence appears for a Kr‐L component, and the nucleosynthetic contribution to argon becomes much smaller. After correction for cosmogenic neon inherited from the host meteorites, the neon in presolar diamonds shows evidence for pre‐irradiation, perhaps in interstellar space, and a nucleosynthetic component perhaps consistent with a supernova source. After a similar correction, helium also shows evidence for presolar irradiation and/or a nucleosynthetic component. For the case of presolar irradiation, due to the small size of the diamonds, a large entity must have been irradiated and recoiling product nuclei collected by the nanodiamonds. The high ³He/²¹Ne ratio (?43) calls for a target with a (C + O)/heavier‐element ratio higher than in chondritic abundances. Bulk gas + dust (cosmic abundances) meet this criteria, as would solids enriched in carbonaceous material. The long recoil range of cosmogenic ³He argues against a specific phase. The excess ³He in presolar diamonds may represent trapped cosmic rays rather than cosmogenic ³He produced in the vicinity of the diamond crystals.     

Effects of aqueous alteration on primordial noble gases and presolar SiC in the carbonaceous chondrite Tagish Lake

Effects of aqueous alteration on primordial noble gas carriers were investigated by analyzing noble gases and determining presolar SiC abundances in insoluble organic matter (IOM) from four Tagish Lake meteorite (C2‐ung.) samples that experienced different degrees of aqueous alteration. The samples contained a mixture of primordial noble gases from phase Q and presolar nanodiamonds (HL, P3), SiC (Ne‐E[H]), and graphite (Ne‐E[L]). The second most altered sample (11i) had a ~2–3 times higher Ne‐E concentration than the other samples. The presolar SiC abundances in the samples were determined from NanoSIMS ion images and 11i had a SiC abundance twice that of the other samples. The heterogeneous distribution of SiC grains could be inherited from heterogeneous accretion or parent body alteration could have redistributed SiC grains. Closed system step etching (CSSE) was used to study noble gases in HNO₃‐susceptible phases in the most and least altered samples. All Ne‐E carried by presolar SiC grains in the most altered sample was released during CSSE, while only a fraction of the Ne‐E was released from the least altered sample. This increased susceptibility to HNO₃ likely represents a step toward degassing. Presolar graphite appears to have been partially degassed during aqueous alteration. Differences in the ⁴He/³⁶Ar and ²⁰Ne/³⁶Ar ratios in gases released during CSSE could be due to gas release from presolar nanodiamonds, with more He and Ne being released in the more aqueously altered sample. Aqueous alteration changes the properties of presolar grains so that they react similar to phase Q in the laboratory, thereby altering the perceived composition of Q.     

Presolar silicon carbide grains and their parent stars

Abstract— Carbon stars are an important source of presolar TiC, SiC, and graphite grains found in meteorites. The elemental abundances in the stellar sources of the SiC grains are inferred by using condensation calculations. These elemental abundances, together with C isotopic compositions, are used to identify possible groups of carbon stars that may have contributed SiC grains to the presolar dust cloud. The most likely parent stars of meteoritic SiC mainstream grains are N-type carbon stars and evolved subgiant CH stars. Both have s-process element abundances higher than solar and 10 < ¹²C/¹³C < 100 ratios. The J stars and giant CH stars, with solar and greater than solar abundances of s-process elements, respectively, are good candidate parents for the ‘A’ and ‘B’ SiC grains with low ¹²C/¹³C ratios. A special subgroup of CH giant stars with very large ¹²C/¹³C ratios could have parented the ‘Y’ SiC grains with ¹²C/¹³C ratios > 100. The carbon star population (e.g., N, R, J, CH groups) needed to provide the observed SiC grains is compared to the current population of carbon stars. This comparison suggests that low-metallicity CH stars may have been more abundant in the past (>4.5 Ga ago) than at present. This suggestion is also supported by condensation-chemistry modeling of the trace element patterns in the SiC grains that shows that subsolar Fe abundances may be required in the stellar sources for many SiC grains. The results of this study suggest that presolar SiC grains in meteorites can provide information about carbon stars during galactic evolution.     

Evidence for lithium and boron from star‐forming regions implanted in presolar SiC grains

Abstract— We report the first measurements of lithium and boron isotope ratios and abundances measured in “gently separated” presolar SiC grains. Almost all analyses of presolar SiC grains since their first isolation in 1987 have been obtained from grains that were separated from their host meteorite by harsh acid dissolution. We recently reported a new method of “gently” separating the grains from meteorites by using freeze‐thaw disaggregation, size, and density separation to retain any nonrefractory coatings or alteration to the surfaces of the grains that have been acquired in interstellar space. Nonrefractory coats or amorphized surfaces will almost certainly be removed or altered by the traditional acid separation procedure. High Li/Si and B/Si ratios of up to ～10^?2 were found implanted in the outer 0.5 μm of the grains dropping to ～10^?5 in the core of the grains. ⁷Li/⁶Li and ¹¹B/¹⁰B ratios indistinguishable from solar system average values were found. Analyses obtained from SiC grains from the acid dissolution technique showed isotope ratios that were the same as those of gently separated grains, but depth profiles that were different. These results are interpreted as evidence of implantation of high velocity (1200–1800 km s^?1) Li and B ions into the grains by shock waves as the grains traveled through star‐forming regions some time after their condensation in the outflow of an AGB star that was their progenitor. The results are in line with spectroscopic measurements of Li and B isotope ratios in star‐forming regions and may be used to infer abundances and isotopic sources in these regions.     

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.     

Light dement geochemistry of the Tagish Lake CI2 chondrite: Comparison with CI1 and CM2 meteorites

Abstract— We have studied the carbon and nitrogen stable isotope geochemistry of a small pristine sample of the Tagish Lake carbonaceous chondrite by high‐resolution stepped‐combustion mass spectrometry, and compared the results with data from the Orgueil (CI1), Elephant Moraine (EET) 83334 (CM1) and Murchison (CM2) chondrites. The small chip of Tagish Lake analysed herein had a higher carbon abundance (5.81 wt%) than any other chondrite, and a nitrogen content (?1220 ppm) between that of CI1 and CM2 chondrites. Owing to the heterogeneous nature of the meteorite, the measured carbon abundance might be artificially high: the carbon inventory and whole‐rock carbon isotopic composition (δ¹³C ? +24.4%_o) of the chip was dominated by ¹³C‐enriched carbon from the decomposition of carbonates (between 1.29 and 2.69 wt%; δ¹³C ? +67%_o and δ¹⁸O ? +35%_o, in the proportions ?4:1 dolomite to calcite). In addition to carbonates, Tagish Lake contains organic carbon (?2.6 wt%, δ¹³C ? ?9%_o; 1033 ppm N, δ¹⁵N ? +77%_o), a level intermediate between CI and CM chondrites. Around 2% of the organic material is thermally labile and solvent soluble. A further ?18% of the organic species are liberated by acid hydrolysis. Tagish Lake also contains a complement of presolar grains. It has a higher nanodiamond abundance (approximately 3650–4330 ppm) than other carbonaceous chondrites, along with ?8 ppm silicon carbide. Whilst carbon and nitrogen isotope geochemistry is not diagnostic, the data are consistent with classification of Tagish Lake as a CI2 chondrite.     

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

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

Compound‐specific carbon isotope compositions of aldehydes and ketones in the Murchison meteorite

Compound‐specific carbon isotope analysis (δ¹³C) of meteoritic organic compounds can be used to elucidate the abiotic chemical reactions involved in their synthesis. The soluble organic content of the Murchison carbonaceous chondrite has been extensively investigated over the years, with a focus on the origins of amino acids and the potential role of Strecker‐cyanohydrin synthesis in the early solar system. Previous δ¹³C investigations have targeted α‐amino acid and α‐hydroxy acid Strecker products and reactant HCN; however, δ¹³C values for meteoritic aldehydes and ketones (Strecker precursors) have not yet been reported. As such, the distribution of aldehydes and ketones in the cosmos and their role in prebiotic reactions have not been fully investigated. Here, we have applied an optimized O‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine (PFBHA) derivatization procedure to the extraction, identification, and δ¹³C analysis of carbonyl compounds in the Murchison meteorite. A suite of aldehydes and ketones, dominated by acetaldehyde, propionaldehyde, and acetone, were detected in the sample. δ¹³C values, ranging from ?10.0‰ to +66.4‰, were more ¹³C‐depleted than would be expected for aldehydes and ketones derived from the interstellar medium, based on interstellar ¹²C/¹³C ratios. These relatively ¹³C‐depleted values suggest that chemical processes taking place in asteroid parent bodies (e.g., oxidation of the IOM) may provide a secondary source of aldehydes and ketones in the solar system. Comparisons between δ¹³C compositions of meteoritic aldehydes and ketones and other organic compound classes were used to evaluate potential structural relationships and associated reactions, including Strecker synthesis and alteration‐driven chemical pathways.     

Coordinated EDX and micro‐Raman analysis of presolar silicon carbide: A novel,nondestructive method to identify rare subgroup SiC

We report the development of a novel method to nondestructively identify presolar silicon carbide (SiC) grains with high initial ²⁶Al/²⁷Al ratios (>0.01) and extreme ¹³C‐enrichments (¹²C/¹³C ≤ 10) by backscattered electron‐energy dispersive X‐ray (EDX) and micro‐Raman analyses. Our survey of a large number of presolar SiC demonstrates that (1) ~80% of core‐collapse supernova and putative nova SiC can be identified by quantitative EDX and Raman analyses with >70% confidence; (2) ~90% of presolar SiC are predominantly 3C‐SiC, as indicated by their Raman transverse optical (TO) peak position and width; (3) presolar 3C‐SiC with ¹²C/¹³C ≤ 10 show lower Raman TO phonon frequencies compared to mainstream 3C‐SiC. The downward shifted phonon frequencies of the ¹³C‐enriched SiC with concomitant peak broadening are a natural consequence of isotope substitution. ¹³C‐enriched SiC can therefore be identified by micro‐Raman analysis; (4) larger shifts in the Raman TO peak position and width indicate deviations from the ideal 3C structure, including rare polytypes. Coordinated transmission electron microscopy analysis of one X and one mainstream SiC grain found them to be of 6H and 15R polytypes, respectively; (5) our correlated Raman and NanoSIMS study of mainstream SiC shows that high nitrogen content is a dominant factor in causing mainstream SiC Raman peak broadening without significant peak shifts; and (6) we found that the SiC condensation conditions in different stellar sites are astonishingly similar, except for X grains, which often condensed more rapidly and at higher atmospheric densities and temperatures, resulting in a higher fraction of grains with much downward shifted and broadened Raman TO peaks.     

Isotopically anomalous neon in meteoritic nanodiamonds: Formation during type II supernova explosions

We hypothesize the formation of neon associated with isotopically anomalous xenon (Xe-HL) in meteoritic nanodiamonds and designated as Ne-X through the mixing of the Ne-HL and Ne-S subcomponents. The Ne-HL subcomponent is neon from the helium (He/C) zone of a type II supernova or a mixture of neon from this zone and its hydrogen zone, while the Ne-S subcomponent is spallation neon formed during a supernova explosion in nuclear spallation reactions induced by high-energy protons. Based on this hypothesis and the presumed abundances of neon isotopes in the zones of a high-mass (25M _⊙) supernova after its explosion, we have calculated the abundances of neon components in nanodiamond separates and its grain-size fractions. Our calculations have shown the following. (1) The main source of Ne-HL is neon from the helium zone of the supernova; as a result, the ²⁰Ne/²²Ne and ²¹Ne/²²Ne ratios for Ne-X are 0.26 ± 0.03 and 0.19 ± 0.04, respectively. The isotopic composition of Ne-X is identical to that for Ne-A2 if Ne-HL is produced by the mixing of neon from the helium and hydrogen zones in proportion 1: 1.06. (2) In meteoritic nanodiamonds, the main neon abundance is determined by neon of the P3 component (Ne-P3). Ne-P3 is retained during thermal metamorphism, because it is sited in traps of the crystal lattice of diamond with a high energy of its activation. (3) The Ne-X/Ne-P3 ratio increases with nanodiamond grain size; as a result, there is no need to invoke an additional neon component (Ne-P6) to interpret the data on neon in meteoritic nanodiamonds.     

Spallation recoil and age of presolar grains in meteorites

Abstract— We have determined the recoil losses from silicon carbide (SiC) grain‐size fractions of spallation Ne produced by irradiation with 1.6 GeV protons. During the irradiation, the SiC grains were dispersed in paraffin wax in order to avoid reimplantation into neighboring grains. Analysis for spallogenic ²¹Ne of grain‐size separates in the size range 0.3 to 6 μm and comparison with the ²²Na activity of the SiC + paraffin mixture indicates an effective recoil range of 2–3 μm with no apparent effect from acid treatments, which are routinely used in the isolation of meteoritic SiC grains. Our results indicate that the majority of presolar SiC grains in primitive meteorites, which are micrometer‐sized, will have lost essentially all spallogenic Ne produced by cosmic‐ray interaction in the interstellar medium. This argues against the validity of previously published presolar ages of Murchison SiC (～10 to ～130 Ma, increasing with grain size; Lewis et al., 1994), where recoil losses had been based on calculated recoil energies. It is argued that the observed variations in meteoritic SiC grain‐size fractions of ²¹Ne/²²Ne ratios are more likely due to the effects of nucleosynthesis in the He‐burning shell of the parent AGB stars which imposes new boundary conditions on nuclear parameters and stellar models. It is suggested that spallation‐Xe produced on the abundant Ba and REE in presolar SiC, rather than spallogenic Ne, may be a promising approach to the presolar age problem. There is a hint in the currently available Xe data (Lewis et al., 1994) that the large (>1 μm) grains may be younger than the smaller (<1 μm) grains. The retention of spallogenic ²¹Ne produced by the bombardment of SiC grains of different grain sizes with 1.6 GeV protons, avoiding reimplantation into neighboring grains by dispersing the SiC grains in paraffin wax, has been derived from a comparison of mass spectrometrically determined ²¹Ne, retained in the grains, with the ²²Na activity of the grains‐plus‐paraffin mixture. Compared to estimates of retention used in previous attempts to determine presolar ages for SiC (Tang and Anders, 1988b; Lewis et al., 1990, 1994), the results indicate significantly lower values. They do, however, agree with retention as expected from previous measurements of recoil ranges in similar systems (Nyquist et al., 1973; Steinberg and Winsberg, 1974). The prime reason for the discrepancy must lie in the energy of the recoiling nuclei entering in the calculation of retention by Tang and Anders (1988b), which is based on considerations by Ray and Völk (1983). Based on the results, it appears questionable that spallation contributes significantly to the observed variations of ²¹Ne/²²Ne ratios among various SiC grain‐size separates (Lewis et al., 1994). We rather suggest that the variations, just as it has been observed for Kr and Ba already (Lewis et al., 1994; Prombo et al., 1993), have a nucleosynthetic origin. Confirmation needs input of improved nuclear data and stellar models into new network calculations of the nucleosynthesis in AGB stars of elements in the Ne region. Finally we argue that, to determine presolar system irradiation effects, spallation Xe is more favorable than is Ne, primarily because of smaller recoil losses for Xe. Although preliminary estimates hint at the possibility that the larger (>1 μm) grains are younger than the smaller (<1 μm) ones, the major uncertainty for a quantitative evaluation lies in the exact composition of the Xe‐N component thought to originate from the envelope of the SiC grains' parent stars.     

Confirmation of a meteoritic component in impact‐melt rocks of the Chesapeake Bay impact structure,Virginia, USA—Evidence from osmium isotopic and PGE systematics

Abstract— The osmium isotope ratios and platinum‐group element (PGE) concentrations of impact‐melt rocks in the Chesapeake Bay impact structure were determined. The impact‐melt rocks come from the cored part of a lower‐crater section of suevitic crystalline‐clast breccia in an 823 m scientific test hole over the central uplift at Cape Charles, Virginia. The ¹⁸⁷Os/¹⁸⁸Os ratios of impact‐melt rocks range from 0.151 to 0.518. The rhenium and platinum‐group element (PGE) concentrations of these rocks are 30–270x higher than concentrations in basement gneiss, and together with the osmium isotopes indicate a substantial meteoritic component in some impact‐melt rocks. Because the PGE abundances in the impact‐melt rocks are dominated by the target materials, interelemental ratios of the impact‐melt rocks are highly variable and nonchondritic. The chemical nature of the projectile for the Chesapeake Bay impact structure cannot be constrained at this time. Model mixing calculations between chondritic and crustal components suggest that most impact‐melt rocks include a bulk meteoritic component of 0.01–0.1% by mass. Several impact‐melt rocks with lowest initial ¹⁸⁷Os/¹⁸⁸Os ratios and the highest osmium concentrations could have been produced by additions of 0.1%–0.2% of a meteoritic component. In these samples, as much as 70% of the total Os may be of meteoritic origin. At the calculated proportions of a meteoritic component (0.01–0.1% by mass), no mixtures of the investigated target rocks and sediments can reproduce the observed PGE abundances of the impact‐melt rocks, suggesting that other PGE enrichment processes operated along with the meteoritic contamination. Possible explanations are 1) participation of unsampled target materials with high PGE abundances in the impact‐melt rocks, and 2) variable fractionations of PGE during syn‐ to post‐impact events.     

Evaporation of nebular fines during chondrule formation

Studies of matrix in primitive chondrites provide our only detailed information about the fine fraction (diameter <2 μm) of solids in the solar nebula. A minor fraction of the fines, the presolar grains, offers information about the kinds of materials present in the molecular cloud that spawned the Solar System. Although some researchers have argued that chondritic matrix is relatively unaltered presolar matter, meteoritic chondrules bear witness to multiple high-temperature events each of which would have evaporated those fines that were inside the high-temperature fluid. Because heat is mainly transferred into the interior of chondrules by conduction, the surface temperatures of chondrules were probably at or above 2000 K. In contrast, the evaporation of mafic silicates in a canonical solar nebula occurs at around 1300 K and FeO-rich, amorphous, fine matrix evaporates at still lower temperatures, perhaps near 1200 K. Thus, during chondrule formation, the temperature of the placental bath was probably >700 K higher than the evaporation temperatures of nebular fines. The scale of chondrule forming events is not known. The currently popular shock models have typical scales of about ¹⁰⁵ km. The scale of nebular lightning is less well defined, but is certainly much smaller, perhaps in the range 1 to 1000 m. In both cases the temperature pulses were long enough to evaporate submicrometer nebular fines. This interpretation disagrees with common views that meteoritic matrix is largely presolar in character and CI-chondrite-like in composition. It is inevitable that presolar grains (both those recognized by their anomalous isotopic compositions and those having solar-like compositions) that were within the hot fluid would also have evaporated. Chondrule formation appears to have continued down to the temperatures at which planetesimals formed, possibly around 250 K. At temperatures >600 K, the main form of C is gaseous CO. Although the conversion of CO to CH₄ at lower temperatures is kinetically inhibited, radiation associated with chondrule formation would have accelerated the conversion. There is now evidence that an appreciable fraction of the nanodiamonds previously held to be presolar were actually formed in the solar nebula. Industrial condensation of diamonds from mixtures of CH₄ and H₂ implies that high nebular CH₄/CO ratios favored nanodiamond formation. A large fraction of chondritic insoluble organic matter may have formed in related processes. At low nebular temperatures appreciable water should have been incorporated into the smoke that condensed following dust (and some chondrule) evaporation. If chondrule formation continued down to temperatures as low as 250 K this process could account for the water concentration observed in primitive chondrites such as LL3.0 and CO3.0 chondrites. Higher H₂O contents in CM and CI chondrites may reflect asteroidal redistribution. In some chondrite groups (e.g., CR) the Mg/Si ratio of matrix material is appreciably (30%) lower than that of chondrules but the bulk Mg/Si ratio is roughly similar to the CI or solar ratio. This has been interpreted as a kind of closed-system behavior sometimes called “complementarity.” This leads to the conclusion that nebular fines were efficiently agglomerated. Its importance, however is obscured by the observation that bulk Mg/Si ratios in ordinary and enstatite chondrites are much lower than those in carbonaceous chondrites, and thus that complementarity did not hold throughout the solar nebula.     

Stardust in Antarctic micrometeorites

Abstract— We report the discovery of presolar silicate, oxide (hibonite), and (possibly) SiC grains in four Antarctic micrometeorites (AMMs). The oxygen isotopic compositions of the eighteen presolar silicate (and one oxide) grains found are similar those observed previously in primitive meteorites and interplanetary dust particles, and indicate origins in oxygen‐rich red giant or asymptotic giant branch stars, or in supernovae. Four grains with anomalous C isotopic compositions were also detected. ¹²C/¹³C as well as Si ratios are similar to those of mainstream SiC grains; the N isotopic composition of one grain is also consistent with a mainstream SiC classification. Presolar silicate grains were found in three of the seven AMMs studied, and are heterogeneously distributed within these micrometeorites. Fourteen of the 18 presolar silicate grains and 3 of the 4 C‐anomalous grains were found within one AMM, T98G8. Presolar silicate‐bearing micrometeorites contain crystalline silicates that give sharp X‐ray diffractions and do not contain magnesiowüstite, which forms mainly through the decomposition of phyllosilicates and carbonates. The occurrence of this mineral in AMMs without presolar silicates suggests that secondary parent body processes probably determine the presence or absence of presolar silicates in Antarctic micrometeorites.     

Constraining the 13C neutron source in AGB stars through isotopic analysis of trace elements in presolar SiC

Abstract— Analyses of the isotopic compositions of multiple elements (Mo, Zr, and Ba) in individual mainstream presolar SiC grains were done by resonant ionization mass spectrometry (RIMS). While most heavy element compositions were consistent with model predictions for the slow neutron capture process (s‐process) in low‐mass (1.5–3 M_⊙) asymptotic giant branch stars of solar metallicity when viewed on single‐element three‐isotope plots, grains with compositions deviating from model predictions were identified on multi‐element plots. These grains have compositions that cannot result from any neutron capture process but can be explained by contamination in some elements with solar system material. Previous work in which only one heavy element per grain was examined has been unable to identify contaminated grains. The multi‐element analyses of this study detected contaminated grains which were subsequently eliminated from consideration. The uncontaminated grains form a data set with a greatly reduced spread on the three‐isotope plots of each element measured, corresponding to a smaller range of ¹³C pocket efficiencies in parent AGB stars. Furthermore, due to this reduced spread, the nature of the stellar starting material, previously interpreted as having solar isotopic composition, is uncertain. The constraint on ¹³C pocket efficiencies in parent stars of these grains may help uncover the mechanism responsible for formation of ¹³C, the primary neutron source for s‐process nucleosynthesis in low‐mass stars.     

Ionized nitrogen mono‐hydride bands are identified in the presolar and carbonado diamond spectra

Abstract– None of the well‐established nitrogen‐related IR absorption bands, common in synthetic and terrestrial diamonds, have been identified in the presolar diamond spectra. In the carbonado diamond spectra, only the single nitrogen impurity (C center) is identified and the assignments of the rest of the nitrogen‐related bands are still debated. It is speculated that the unidentified bands in the nitrogen absorption region are not induced by nitrogen, but rather by nitrogen‐hydrides because in the interstellar environment, nitrogen reacts with hydrogen and forms NH⁺; NH; NH₂; NH_3. Among these hydrides, the electronic configuration of NH⁺ is the closest to carbon. Thus, this ionized nitrogen‐mono‐hydride is the best candidate to substitute carbon in the diamond structure. The bands of the substitutional NH⁺ defect are deduced by redshifting the irradiation‐induced N⁺ bands due to the mass of the additional hydrogen. The six bands of the NH⁺ defects are identified in both the presolar and the carbonado diamond spectra. The new assignments identify all of the nitrogen‐related bands in the spectra, indicating that presolar and carbonado diamonds contain only single nitrogen impurities.     

Iron isotopic measurements in presolar silicate and oxide grains from the Acfer 094 ungrouped carbonaceous chondrite

We carried out Fe isotopic analyses on 21 O‐rich presolar grains from the Acfer 094 ungrouped carbonaceous chondrite. Presolar grains were identified on the basis of oxygen isotopic ratios, and elemental compositions were measured by Auger spectroscopy. The Fe isotopic measurements were carried out by analyzing the Fe isotopes as negative secondary oxides with the NanoSIMS to take advantage of the higher spatial resolution of the Cs⁺ primary ion beam. Our results demonstrate the effectiveness of this approach for measuring both ⁵⁴Fe/⁵⁶Fe and ⁵⁷Fe/⁵⁶Fe. The ion yield for FeO^– is significantly lower than for Fe⁺, but this is not a serious limitation for presolar silicate grains with Fe as a major element. Most of the grains analyzed are ferromagnesian silicates, but we also measured four oxide grains. Iron contents are high in all of the grains, ranging from 10 to 40 atom%. Three of the grains belong to oxygen isotope Group 4. All of them have ⁵⁴Fe/⁵⁶Fe and ⁵⁷Fe/⁵⁶Fe ratios that are solar within errors, consistent with an origin in the outer zones of a Type II supernova, as indicated by their oxygen isotopic compositions. The remaining grains belong to oxygen isotope Group 1, with origins in low‐mass AGB stars. The majority of these also have solar ⁵⁴Fe/⁵⁶Fe and ⁵⁷Fe/⁵⁶Fe ratios. However, four grains are depleted in ⁵⁷Fe; one is also slightly depleted in ⁵⁴Fe. Current AGB models predict excesses in ⁵⁷Fe with ⁵⁴Fe/⁵⁶Fe ratios that largely reflect the metallicity of the parent star. While the solar ⁵⁷Fe/⁵⁶Fe ratios are consistent with formation of the grains in early third dredge‐up episodes, these models cannot account for the grains with ⁵⁷Fe depletions. Comparison with galactic evolution models suggests formation of these grains from stars with significantly subsolar metallicity; however, these models also predict large depletions in ⁵⁴Fe, which are not observed in the grains. Thus, the isotopic compositions of these grains remain unexplained.     

Oxygen isotopic compositions and origins of calcium‐aluminum‐rich inclusions and chondrules

Abstract— Primary minerals in calcium‐aluminum‐rich inclusions (CAIs), Al‐rich and ferromagnesian chondrules in each chondrite group have δ¹⁸O values that typically range from ?50 to +5%0. Neglecting effects due to minor mass fractionations, the oxygen isotopic data for each chondrite group and for micrometeorites define lines on the three‐isotope plot with slopes of 1.01 ± 0.06 and intercepts of ?2 ± 1. This suggests that the same kind of nebular process produced the ¹⁶O variations among chondrules and CAIs in all groups. Chemical and isotopic properties of some CAIs and chondrules strongly suggest that they formed from solar nebula condensates. This is incompatible with the existing two‐component model for oxygen isotopes in which chondrules and CAIs were derived from heated and melted ¹⁶O‐rich presolar dust that exchanged oxygen with ¹⁶O‐poor nebular gas. Some FUN CAIs (inclusions with isotope anomalies due to fractionation and unknown nuclear effects) have chemical and isotopic compositions indicating they are evaporative residues of presolar material, which is incompatible with ¹⁶O fractionation during mass‐independent gas phase reactions in the solar nebula. There is only one plausible reason why solar nebula condensates and evaporative residues of presolar materials are both enriched in ¹⁶O. Condensation must have occurred in a nebular region where the oxygen was largely derived from evaporated ¹⁶O‐rich dust. A simple model suggests that dust was enriched (or gas was depleted) relative to cosmic proportions by factors of ～10 to >50 prior to condensation for most CAIs and factors of 1–5 for chondrule precursor material. We infer that dust‐gas fractionation prior to evaporation and condensation was more important in establishing the oxygen isotopic composition of CAIs and chondrules than any subsequent exchange with nebular gases. Dust‐gas fractionation may have occurred near the inner edge of the disk where nebular gases accreted into the protosun and Shu and colleagues suggest that CAIs formed.