Sulfur in presolar silicon carbide grains from asymptotic giant branch stars

We studied 14 presolar SiC mainstream grains for C‐, Si‐, and S‐isotopic compositions and S elemental abundances. Ten grains have low levels of S contamination and CI chondrite‐normalized S/Si ratios between 2 × 10^?5 and 2 × 10^?4. All grains have S‐isotopic compositions compatible within 2σ of solar values. Their mean S isotope composition deviates from solar by at most a few percent, and is consistent with values observed for the carbon star IRC+10216, believed to be a representative source star of the grains, and the interstellar medium. The isotopic data are also consistent with stellar model predictions of low‐mass asymptotic giant branch (AGB) stars. In a δ³³S versus δ³⁴S plot the data fit along a line with a slope of 1.8 ± 0.7, suggesting imprints from galactic chemical evolution. The observed S abundances are lower than expected from equilibrium condensation of CaS in solid solution with SiC under pressure and temperature conditions inferred from the abundances of more refractory elements in SiC. Calcium to S abundance ratios are generally above unity, contrary to expectations for stoichiometric CaS solution in the grains, possibly due to condensation of CaC₂ into SiC. We observed a correlation between Mg and S abundances suggesting solid solution of MgS in SiC. The low abundances of S in mainstream grains support the view that the significantly higher abundances of excess ³²S found in some Type AB SiC grains are the result of in situ decay of radioactive ³²Si from born‐again AGB stars that condensed into AB grains.     

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.     

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.     

Trace element depth profiles in presolar silicon carbide grains

Abstract– We have analyzed eleven presolar SiC grains from the Murchison meteorite using time‐of‐flight secondary ion mass spectrometry. The Si isotopic compositions of the grains indicate that they are probably of an AGB star origin. The average abundances of Mg, Fe, Ca, Al, Ti, and V are strongly influenced by their condensation behavior into SiC in circumstellar environments. Depth profiles of Li, B, Mg, Al, K, Ca, Ti, V, Cr, and Fe in the SiC grains show that trace elements are not always homogenously distributed. In approximately half of the SiC grains studied here, the trace element distributions can be explained by condensation processes around the grains’ parent stars. These grains appear to have experienced only minimal processing before their arrival in the presolar molecular cloud, possibly due to short residence times in the interstellar medium. The remaining SiC grains contained elevated abundances of several elements within their outer 200 nm, which is attributed to the implantation of energetic ions accelerated by shockwaves in the interstellar medium. These grains may have spent a longer period of time in this region, hence increasing the probability of them passing through a shockfront. Distinct groups of presolar SiC grains whose residence times in the interstellar medium differ are consistent with previous findings based on noble gas studies, although some grains may also have been shielded from secondary alteration by protective outer mantles.     

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.     

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.     

The effects of secondary processing in the unique carbonaceous chondrite Miller Range 07687

Our detailed mineralogical, elemental, and isotopic study of the Miller Range (MIL) 07687 meteorite showed that, although this meteorite has affinities to CO chondrites, it also exhibits sufficient differences to warrant classification as an ungrouped carbonaceous chondrite. The most notable feature of MIL 07687 is the presence of two distinct matrix lithologies that result from highly localized aqueous alteration. One of these lithologies is Fe‐rich and exhibits evidence for interaction with water, including the presence of fibrous (dendritic) ferrihydrite. The other lithology, which is Fe‐poor, appears to represent relatively unaltered protolith material. MIL 07687 has presolar grain abundances consistent with those observed in other modestly altered carbonaceous chondrites: the overall abundance of O‐rich presolar grains is 137 ± 3 ppm and the overall abundance of SiC grains is 71 ± 11 ppm. However, there is a large difference in the observed O‐rich and SiC grain number densities between altered and unaltered areas, reflecting partial destruction of presolar grains (both O‐ and C‐rich grains) due to the aqueous alteration experienced by MIL 07687 under highly oxidizing conditions. Detailed coordinated NanoSIMS‐TEM analysis of a large hotspot composed of an isotopically normal core surrounded by a rim composed of ¹⁷O‐rich grains is consistent with either original condensation of the core and surrounding grains in the same parent AGB star, or with grain accretion in the ISM or solar nebula.     

Isotopic properties of silicon carbide X grains from the Murchison meteorite in the size range 0.5‐1.5 μm

Abstract— We report isotopic abundances for C, N, Mg‐Al, Si, Ca‐Ti, and Fe in 99 presolar silicon carbide (SiC) grains of type X (84 grains from this work and 15 grains from previous studies) from the Murchison CM2 meteorite, ranging in size from 0.5 to 1.5 μm. Carbon was measured in 41 X grains, n in 37 grains, Mg‐Al in 18 grains, Si in 87 grains, Ca‐Ti in 25 grains, and Fe in 8 grains. These X grains have ¹²C/¹³C ratios between 18 and 6800, ¹⁴N/¹⁵n ratios from 13 to 200, δ²⁹Si/²⁸Si between ?750 and +60%₀, δ³⁰Si/²⁸Si from ?770 to ?10%₀, and ⁵⁴Fe/⁵⁶Fe ratios that are compatible with solar within the analytical uncertainties of several tens of percent. Many X grains carry large amounts of radiogenic ²⁶Mg (from the radioactive decay of ²⁶Al, half‐life ? 7 times 10⁵ years) and radiogenic ⁴⁴Ca (from the radioactive decay of ⁴⁴Ti, half‐life = 60 years). While all X grains but one have radiogenic ²⁶Mg, only ～20% of them have detectable amounts of radiogenic ⁴⁴Ca. Initial ²⁶Al/²⁷Al ratios of up to 0.36 and initial ⁴⁴Ti/⁴⁸Ti ratios of up to 0.56 can be inferred. The isotopic data are compared with those expected from the potential stellar sources of SiC dust. Carbon stars, Wolf‐Rayet stars, and novae are ruled out as stellar sources of the X grains. The isotopic compositions of C and Fe and abundances of extinct ⁴⁴Ti are well explained both by type Ia and type II supernova (SN) models. The same holds for ²⁶Al/²⁷Al ratios, except for the highest ²⁶Al/²⁷Al ratios of >0.2 in some X grains. Silicon agrees qualitatively with SN model predictions, but the observed ²⁹Si/³⁰Si ratios in the X grains are in most cases too high, pointing to deficiencies in the current understanding of the production of Si in SN environments. The measured ¹⁴n/¹⁵n ratios are lower than those expected from SN mixing models. This problem can be overcome in a 15 M_odot; type II SN if rotational mixing, preferential trapping of N, or both from ¹⁵n‐rich regions in the ejecta are considered. The isotopic characteristics of C, N, Si, and initial ²⁶Al/²⁷Al ratios in small X grains are remarkably similar to those of large X grains (2–10 μm). Titanium‐44 concentrations are generally much higher in smaller grains, indicative of the presence of Ti‐bearing subgrains that might have served as condensation nuclei for SiC. The fraction of X grains among presolar SiC is largely independent of grain size. This implies similar grain‐size distributions for SiC from carbon stars (mainstream grains) and supernovae (X grains), a surprising conclusion in view of the different conditions for dust formation in these two types of stellar sources.     

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.     

Survival of refractory presolar grain analogs during Stardust‐like impact into Al foils: Implications for Wild 2 presolar grain abundances and study of the cometary fine fraction

We present results of FIB–TEM studies of 12 Stardust analog Al foil craters which were created by firing refractory Si and Ti carbide and nitride grains into Al foils at 6.05 km s^?1 with a light‐gas gun to simulate capture of cometary grains by the Stardust mission. These foils were prepared primarily to understand the low presolar grain abundances (both SiC and silicates) measured by SIMS in Stardust Al foil samples. Our results demonstrate the intact survival of submicron SiC, TiC, TiN, and less‐refractory Si₃N₄ grains. In small (<2 μm) craters that are formed by single grain impacts, the entire impacting crystalline grain is often preserved intact with minimal modification. While they also survive in crystalline form, grains at the bottom of larger craters (>5 μm) are typically fragmented and are somewhat flattened in the direction of impact due to partial melting and/or plastic deformation. The low presolar grain abundance estimates derived from SIMS measurements of large craters (mostly >50 μm) likely result from greater modification of these impactors (i.e., melting and isotopic dilution), due to higher peak temperatures/pressures in these crater impacts. The better survivability of grains in smaller craters suggests that more accurate presolar grain estimates may be achievable through measurement of such craters. It also suggests small craters can provide a complementary method of study of the Wild 2 fine fraction, especially for refractory CAI‐like minerals.     

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.     

A study of presolar material in hydrated lithic clasts from metal-rich carbonaceous chondrites

We report on the investigation of presolar grain inventories of hydrated lithic clasts in three metal-rich carbonaceous chondrites from the CR clan, Acfer 182 (CH3), Isheyevo (CH3/CB_b3), and Lewis Cliff (LEW) 85332 (C3-un), as well as the carbon- and nitrogen-isotopic compositions of the fine-grained clast material. Eleven presolar silicate grains as well as nine presolar silicon carbide (SiC) grains were identified in the clasts. Presolar silicate abundances range from 4 to 22 parts per million (ppm), significantly lower than in pristine meteorites and interplanetary dust particles (IDP), and comparable to recent findings for CM2s and CR2 interchondrule matrix. SiC concentrations lie between 9 and 23 ppm, and are comparable to the values for CI, CM, and CR chondrites. The results of our investigation suggest similar alteration pathways for the clast material, the interchondrule matrix of the CR2 chondrites, and the fine-grained fraction of CM2 chondrites. Fine-grained matter of all three meteorites contains moderate to high ¹⁵N-enrichments (~50‰ ≤ δ¹⁵N ≤ ~1600‰) compared to the terrestrial value, indicating the presence of primitive organic material. We observed no correlation between ¹⁵N-enrichments and presolar dust concentrations in the clasts. This is in contrast to the findings from a suite of primitive IDPs, which display in several cases enhanced bulk ¹⁵N/¹⁴N ratios and high presolar grain abundances of several hundred or even thousand ppm. The bulk ¹⁵N/¹⁴N ratios of the clasts are comparable to the range for primitive IDPs, suggesting a nitrogen carrier less susceptible to destruction by aqueous alteration than silicate stardust.     

The presolar grain inventory of fine‐grained chondrule rims in the Mighei‐type (CM) chondrites

We investigated the inventory of presolar silicate, oxide, and silicon carbide (SiC) grains of fine‐grained chondrule rims in six Mighei‐type (CM) carbonaceous chondrites (Banten, Jbilet Winselwan, Maribo, Murchison, Murray and Yamato 791198), and the CM‐related carbonaceous chondrite Sutter's Mill. Sixteen O‐anomalous grains (nine silicates, six oxides) were detected, corresponding to a combined matrix‐normalized abundance of ~18 ppm, together with 21 presolar SiC grains (~42 ppm). Twelve of the O‐rich grains are enriched in ¹⁷O, and could originate from low‐mass asymptotic giant branch stars. One grain is enriched in ¹⁷O and significantly depleted in ¹⁸O, indicative of additional cool bottom processing or hot bottom burning in its stellar parent, and three grains are of likely core‐collapse supernova origin showing enhanced ¹⁸O/¹⁶O ratios relative to the solar system ratio. We find a presolar silicate/oxide ratio of 1.5, significantly lower than the ratios typically observed for chondritic meteorites. This may indicate a higher degree of aqueous alteration in the studied meteorites, or hint at a heterogeneous distribution of presolar silicates and oxides in the solar nebula. Nevertheless, the low O‐anomalous grain abundance is consistent with aqueous alteration occurring in the protosolar nebula and/or on the respective parent bodies. Six O‐rich presolar grains were studied by Auger Electron Spectroscopy, revealing two Fe‐rich silicates, one forsterite‐like Mg‐rich silicate, two Al‐oxides with spinel‐like compositions, and one Fe‐(Mg‐)oxide. Scanning electron and transmission electron microscopic investigation of a relatively large silicate grain (490 nm × 735 nm) revealed that it was crystalline åkermanite (Ca₂Mg[Si₂O₇]) or a an åkermanite‐diopside (MgCaSi₂O₆) intergrowth.     

Trends in the study of presolar dust grains from primitive meteorites

Abstract— A series of trends can be discerned in the study of presolar dust grains from primitive meteorites, and these trends might give us hints in which direction this new field of astronomy is developing. They include: (1) a focus on ever smaller components of meteorites; (2) a shift from the study of the elemental abundances in the solar system to the study of isotopic abundances; (3) a shift of emphasis from averages of the isotopic abundances as represented by the whole solar system to individual isotopic components preserved in circumstellar dust grains; (4) the preferential study of rare types of presolar dust grains; (5) the emergence of new technical capabilities for the study of individual presolar dust grains; examples include isotopic imaging and resonance ionization mass spectrometry (RIMS); and (6) a shift from a situation in which grain data confirm previously held theoretical ideas to a situation in which the experimental data impose new constraints on theoretical models of nucleosynthesis, stellar mixing and grain formation in stellar outflows. In other words, the data do not confirm but drive the theory. An example is the distribution of Si isotopic ratios in individual mainstream SiC grains for which many different theoretical explanations have been offered. There are still many unsolved problems posed by the grain data, the most difficult being the interpretation of the isotopic ratios of grains with a supernova signature (evidence for ⁴⁴Ti and excesses in ²⁸Si) in terms of theoretical models of nucleosynthesis and the mixing of supernova ejecta. Future progress is expected to come from the analysis of larger numbers of grains, the search for new types of presolar grains, the analysis of smaller grains and of more elements in a given grain, both made possible by the increase in sensitivity of ion microprobes and the extended application of RIMS, from multi-dimensional models of stellar evolution with enlarged nuclear networks, and from new measurements of nuclear cross sections.     

Atom‐probe analyses of nanodiamonds from Allende

Atom‐probe tomography (APT) is currently the only analytical technique that, due to its spatial resolution and detection efficiency, has the potential to measure the carbon isotope ratios of individual nanodiamonds. We describe three different sample preparation protocols that we developed for the APT analysis of meteoritic nanodiamonds at sub‐nm resolution and present carbon isotope peak ratios of meteoritic and synthetic nanodiamonds. The results demonstrate an instrumental bias associated with APT that needs to be quantified and corrected to obtain accurate isotope ratios. After this correction is applied, this technique should allow determination of the distribution of ¹²C/¹³C ratios in individual diamond grains, solving the decades‐old question of the origin of meteoritic nanodiamonds: what fraction, if any, formed in the solar system and in presolar environments? Furthermore, APT could help us identify the stellar sources of any presolar nanodiamonds that are detected.     

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.     

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.     

3‐D elemental and isotopic composition of presolar silicon carbides

Abstract— Thirteen presolar silicon carbide grains—three of supernova (SN) origin and ten of asymptotic giant branch (AGB) star origin—were examined with time‐of‐flight‐secondary ion mass spectrometry (TOF‐SIMS). The grains had been extracted from two different meteorites—Murchison and Tieschitz—using different acid residue methods. At high lateral resolution of ～300 nm, isotopic and elemental heterogeneities within the micrometer‐sized grains were detected. The trace elemental abundances, when displayed in two‐element correlation plots, of Li, Mg, K, and Ca show a clear distinction between the two different meteoritic sources. The different concentrations might be attributed to differences of the host meteorites and/or of extraction methods whereas the stellar source seems to be less decisive. In one SN grain with ²⁶Mg‐enrichment from extinct ²⁶Al, the acid treatment, as part of the grain separation procedure, affected the Mg/Al ratio in the outer rim and therefore the inferred initial ²⁶Al/²⁷Al ratio. A second SN grain exhibits a lateral heterogeneity in ²⁶Al/²⁷Al, which either is due to residual Al‐rich contamination on the grain surface or to the condensation chemistry in the SN ejecta.     

Structural and isotopic microanalysis of presolar SiC from supernovae

Abstract– We report on the microstructure, crystallography, chemistry, and isotopic compositions of seven SiC X grains and two mainstream grains from the Murchison meteorite. TEM crystallographic analysis revealed that the X grains (approximately 3 μm) are composed of many small crystals (24–457 nm), while the similarly sized mainstream grains are composed of only a few crystals (0.5–1.7 μm). The difference in crystal size likely results from differences in their formation environments: the X grain crystals evidently formed under conditions of greater supersaturation and rapid growth compared to their mainstream counterparts. However, the same polytypes are observed in both mainstream and X grains. Six X grains and both mainstream grains are entirely the 3C‐SiC polytype and one X grain is an intergrowth of the 3C‐SiC and 2H‐SiC polytypes. EDXS measurements indicate relatively high Mg content in the X grains (≲5 atomic%), while Mg was undetectable in the mainstream grains. The high Mg content is probably from the decay of ²⁶Al into ²⁶Mg. Estimates of the ²⁶Al/²⁷Al ratios, which range from 0.44–0.67, were made from elemental Mg/Al ratios. This range is consistent with the ²⁶Al/²⁷Al ratios inferred from previous isotopic measurements of X grains. We also report the first direct observations of subgrains in X grains, including the first silicides [(Fe,Ni)_nSi_m]. Diffraction data do not match any previously observed presolar phases, but are a good fit to silicides, which are predicted stable SN condensates. Eight subgrains with highly variable Ni/Fe ratios (0.12–1.60) were observed in two X grains.     

Isotopic compositions of different presolar silicon carbide size fractions from the Murchison meteorite

Abstract— We report measurements of isotopic ratios of C, N, Mg, Si, Ca, Ti, Cr, and Fe in bulk samples (aggregates of many grains) of up to seven different fractions of silicon carbide (SiC), ranging from 0.38 to 3.0μm in diameter, from the Murchison CM2 carbonaceous chondrite. Ratios of ¹²C/¹³C range from 37 to 42 and ¹⁴N/¹⁵N ratios from 370 to 520, within the range of single‐grain measurements on coarser samples and in agreement with an asymptotic giant branch (AGB) star origin of most of the grains. Variations among size fractions do not show any simple trend and can be explained by varying contamination with isotopically normal material. Silicon isotopic ratios vary only little and, with one exception, lie to the right of the singlegrain mainstream correlation line. This might indicate a higher percentage of the minor populations Y and Z among finer grain‐size fractions. All bulk samples have large ²⁶Mg excesses attributed to the presence of short‐lived ²⁶Al at the time of grain formation. Inferred ²⁶Al/²⁷Al ratios are much larger than those measured in single larger mainstream grains. This is probably because of the presence of SiC grains of type X; we obtain an estimate of 0.4 for their ²⁶Al/²⁷Al ratio. Our Ca‐isotopic measurements, the first made on presolar SiC grains, show excesses in ⁴²Ca and ⁴³Ca, which is in general agreement with theoretical expectations for AGB stars. Calcium‐44 excesses are much larger than expected and are probably because of X grains, which have high⁴⁴Ca excesses because of the decay of short‐lived ⁴⁴Ti produced in supernova explosions. We arrive at an estimate of 0.014 for the initial ⁴⁴Ti/⁴⁸Ti ratio of the X grains, within the range obtained from previous single X grain measurements. The Ti‐isotopic ratios of the bulk samples show a V‐shaped pattern with excesses of all isotopes relative to ⁴⁸Ti. Isotopes ⁴⁶Ti, ⁴⁷Ti, and ⁵⁰Ti show excesses relative to the correlation between Ti and Si ratios for single grains and are in general agreement with theoretical models of s‐process nucleosynthesis in AGB stars. In contrast, ⁴⁹Ti does not show any excess relative to the singlegrain data; it also fails to agree with theory, which predicts much larger excesses than observed. Measured ⁵³Cr/⁵²Cr and ⁵⁷Fe/⁵⁶Fe ratios are normal within errors. The first result is expected even for Cr in AGB star envelopes, but the second result suggests that most of the Fe analyzed originates from contamination. We have found no simple trends in isotopic composition with respect to grain size that can be interpreted in terms of nucleosynthetic origin, unlike the results for Kr, Xe, Ba, and Sr.