Thomas J. Bernatowicz

CONSTRAINTS ON STELLAR GRAIN FORMATION FROM PRESOLAR GRAPHITE IN THE MURCHISON METEORITE

We report the results of isotopic, chemical, structural, and crystallographic microanalyses of graphitic spherules (0.3E9 km) extracted from the Murchison meteorite. The spherules have 12C/13C ratios ranging over 3 orders of magnitude (from 0.02 to 80 times solar), clearly establishing their presolar origin as stellar condensates. These and other isotopic constraints point to a variety of stellar types as sources of the carbon, including low-mass asymptotic giant branch (AGB) stars and supernovae. Transmission elec- tron microscopy (TEM) of ultrathin sections of the spherules revealed that many have a composite struc- ture consisting of a core of nanocrystalline carbon surrounded by a mantle of well-graphitized carbon. The nanocrystalline cores are compact masses consisting of randomly oriented graphene sheets, from PAH-sized units up to sheets 3E4 nm in diameter, with little graphitic layering order. These sheets prob- ably condensed as isolated particles that subsequently coalesced to form the cores, after which the sur- rounding graphitic mantles were added by vapor deposition. We also detected internal crystals of metal carbides in one-third of the spherules. These crystals (5E200 nm) have compositions ranging from nearly pure TiC to nearly pure Zr-Mo carbide. Some of these car- bides occur at the centers of the spherules and are surrounded by well-graphitized carbon, having evi- dently served as heterogeneous nucleation centers for condensation of carbon. Others were entrained by carbon as the spherules grew. The chemical and textural evidence indicates that these carbides formed prior to carbon condensation, which indicates that the C/O ratios in the stellar sources were very close to unity. Only one of the 67 spherules studied in the TEM contained SiC, from which we infer that carbon condensation nearly always preceded SiC formation. This observation places stringent limits on the possible delay of graphite formation and is consistent with the predictions of equilibrium thermody- namics in the inferred range of pressure and C/O ratios. We model the formation of the observed refractory carbides under equilibrium conditions, both with and without s-process enrichment of Zr and Mo, and show that the chemical variation among internal crystals is consistent with the predicted equilibrium condensation sequence. The compositions of most of the Zr-Mo-Ti carbides require an s-process enrichment of both Zr and Mo to at least 30 times their solar abundances relative to Ti. However, to account for crystals in which Mo is also enriched relative to Zr, it is necessary to suppose that Zr is removed by separation of the earliest formed ZrC crystals from their parent gas. We also explore the formation constraints imposed by kinetics, equilibrium thermodynamics, and the observation of clusters of carbide crystals in some spherules, and conclude that relatively high formation pressures dynes cm~2), and/or condensable carbon number densities cm~3) are required. (Z0.1 (Z108 The graphite spherules with 12C/13C ratios less than the solar value may have originated in AGB stellar winds. However, in the spherically symmetric AGB atmospheres customarily assumed in models of stellar grain formation, pressures are much too low (by factors of to produce carbide crystals or Z102) graphite spherules of the sizes observed within plausible timescales. If some of the graphite spherules formed in the winds from such stars, it thus appears necessary to assume that the regions of grain forma- tion are density concentrations with length scales less than a stellar radius. Some of the spherules with both 12C/13C ratios greater than the solar value and 28Si excesses probably grew in the ejecta of super- novae. The isotopic compositions and growth constraints imply that they must have formed at high den- sities (e.g., with g cm~3) from mixtures of inner-shell material with material from the C-rich

Genesis of presolar diamonds: Comparative high-resolution transmission electron microscopy study of meteoritic and terrestrial nano-diamonds

Abstract Nano-diamonds isolated from acid dissolution residues of primitive carbonaceous meteorites (Allende and Murchison) were studied using high-resolution transmission electron microscopy. To discriminate among their most likely formation mechanisms, high-pressure shock-induced metamorphism or low-pressure vapor condensation, the microstructures of presolar diamond crystallites were compared to those of (terrestrial) synthesized nano-diamonds. The synthesized diamonds used for comparison in this study were produced by high-pressure shock waves generated in controlled detonations and by direct nucleation and homoepitaxial growth from the vapor phase in low-pressure chemical vapor deposition (CVD)-type processes. Microstructural features were identified that appear unique to shock metamorphism and to nucleation from the vapor phase, respectively. A comparison of these features to the microstructures found in presolar diamonds indicates that the predominant mechanism for presolar diamond formation is a vapor deposition process, suggesting a circumstellar condensation origin. A new presolar grain component has also been identified in the meteoritic residues, the (2H) hexagonal polytype of diamond (lonsdaleite).

Interstellar grains within interstellar grains

Five interstellar graphite spherules extracted from the Murchison carbonaceous meteorite are studied. The isotopic and elemental compositions of individual particles are investigated with the help of an ion microprobe, and this analysis is augmented with structural studies of ultrathin sections of the grain interiors by transmission electron microscopy. As a result, the following procedure for the formation of the interstellar graphite spherule bearing TiC crystals is inferred: (1) high-temperature nucleation and rapid growth of the graphitic carbon spherule in the atmosphere of a carbon-rich star, (2) nucleation and growth of TiC crystals during continued growth of the graphitic spherule and the accretion of TiC onto the spherule, (3) quenching of the graphite growth process by depletion of C or by isolation of the spherule before other grain types could condense.

Solubility and partitioning of Ne, Ar, Kr, and Xe in minerals and synthetic basaltic melts

We have measured the solubilities of Ne, Ar, Kr and Xe in natural samples of anorthite, diopside, forsterite, spinel and in synthetic basaltic melts. The minerals and melts represent equilibrium pairs in the Fo-An-Di-SiO2 system. Samples were suspended in individual crucibles in a one-bar flowing mixed noble gas atmosphere at 1300 or 1332°C for times ranging from 7–18 days. The solubilities in the minerals increase with increasing noble gas atomic number and typical solubility values are surprisingly high. Samples of a particular mineral (i.e., anorthite) that came from different localities yield distinctly different and reproducible solubility values. This indicates that properties intrinsic to individual samples can influence solubility. Noble gases are likely to be sited in lattice vacancy defects. In contrast, the solubilities in the melts decrease with increasing atomic number. Our data overlap the low end of the range defined previously for natural basalts; however, the dynamic range of the values from Ne to Xe is not as great as for the natural melts. Solubilities correlate well with melt molar volume but poorly with density. The partition coefficients increase with increasing noble gas atomic number for all mineral/melt pairs. Such trends imply that the terrestrial planet atmospheres were not derived from partial melting of chondritic source material. Significant fractionation of Kr relative to Xe is not observed, ruling out an origin for Earths “missing” Xe via magmatic fractionation. Partition coefficient absolute values are frequently near or greater than unity. For example, the ranges for five diopside measurements are the following: DNel, 0.013–0.37; DArl, 0.15–0.84; DKrl, 0.31–2.4; and DXel, 3.2–47. This indicates that magmatic transport is not an efficient mechanism for degassing the terrestrial planets. Our results favor a catastrophic origin for the atmospheres.

Presolar Graphite from AGB Stars: Microstructure and s-Process Enrichment

Correlated transmission electron microscopy and secondary ion mass spectrometry with submicron spatial resolution (NanoSIMS) investigations of the same presolar graphites spherules from the Murchison meteorite were conducted, to link the isotopic anomalies with the mineralogy and chemical composition of the graphite and its internal grains. Refractory carbide grains (especially titanium carbide) are commonly found within the graphite spherules, and most have significant concentrations of Zr, Mo, and Ru in solid solution, elements primarily produced by s-process nucleosynthesis. The effect of chemical fractionation on the Mo/Ti ratio in these carbides is limited, and therefore from this ratio one can infer the degree of s-process enrichment in the gas from which the graphite condensed. The resulting s-process enrichments within carbides are large (~200 times solar on average), showing that most of the carbide-containing graphites formed in the mass outflows of asymptotic giant branch (AGB) stars. NanoSIMS measurements of these graphites also show isotopically light carbon (mostly in the 100 < 12C/13C < 400 range). The enrichment of these presolar graphites in both s-process elements and 12C considerably exceeds that astronomically observed around carbon stars. However, a natural correlation exists between 12C and s-process elements, as both form in the He intershell region of thermally pulsing AGB stars and are dredged up together to the surface. Their observation together suggests that these graphites may have formed in chemically and isotopically inhomogeneous regions around AGB stars, such as high-density knots or jets. As shown in the companion paper, a gas density exceeding that expected for smooth mass outflows is required for graphite of the observed size to condense at all in circumstellar environments, and the spatially inhomogeneous, high-density regions from which they condense may also be incompletely mixed with the surrounding gas. We have greatly expanded the available data set of presolar graphites (N = 847) and characterized them by their morphology (onion type and cauliflower type). This effort has also revealed two new, rare presolar phases (iron carbide and metallic osmium). Due to the peculiar gas composition needed to form these rare presolar grain types, the graphites containing them are more likely to originate in supernova outflows.

Structural, chemical, and isotopic microanalytical investigations of graphite from supernovae

Abstract We report the results of coordinated ion microprobe and transmission electron microscope (TEM) studies of presolar graphites from the KE3 separate (1.65–1.72 g/cm3) of the Murchison CM2 meteorite. Isotopic analysis of individual graphites (1–12 μm) with the ion microprobe shows many to have large 18O excesses combined with large silicon isotopic anomalies, indicative of a supernova (SN) origin. Transmission electron microscopy (TEM) of ultramicrotome slices of these SN graphites revealed a high abundance (25–2400 ppm) of internal titanium carbides (TiCs), with a single graphite in some cases containing hundreds of TiCs. Isotopic compositions of individual TiCs by nanoscale resolution secondary ion mass spectrometry (NanoSIMS) confirmed their presolar origin. In addition to TiCs, composite TiC/Fe grains (TiCs with attached iron–nickel subgrains) and solitary kamacite internal grains were found. In the composite grains, the attached iron phase (kamacite [0–24 at. % Ni] or taenite [up to 60 at. % Ni]) was epitaxially grown onto one or more TiC faces. In contrast to the denser Murchison KFC1 graphites, no Zr-Ti-Mo carbides were observed. The average TiC diameters were quite variable among the SN graphites, from 30 to 232 nm, and were generally independent of the host graphite size. TiC grain morphologies ranged from euhedral to anhedral, with the grain surfaces exhibiting variable degrees of corrosion, and sometimes partially amorphous rims (3 to 15 nm thick). Partially amorphous rims of similar thickness were also observed on some solitary kamacite grains. We speculate that the rims on the internal grains are most plausibly the result of atom bombardment caused by drift of grains with respect to the ambient gas, requiring relative outflow speeds ∼100 km/s (i.e., a few percent of the SN mass outflow speed). Energy dispersive X-ray spectrometry (EDXS) of TiCs revealed significant V in solid solution, with an average V/Ti ratio over all TiCs of ∼83% of the solar value of 0.122. Significant variations about the mean V/Ti ratio were also seen among TiCs in the same graphite, likely indicating chemical equilibration with the surrounding gas over a range of temperatures. In general, the diversity in internal TiC properties suggests that TiCs formed first and had substantially diverse histories before incorporation into the graphite, implying some degree of turbulent mixing in the SN outflows. In most graphites, there is a decrease in the number density of TiCs as a function of increasing radial dis- tance, caused by either preferential depletion of TiCs from the gas or an acceleration of graphite growth with decreasing ambient temperature. In several graphites, TiCs showed a trend of larger V/Ti ratios with increasing distance from the graphite center, an indication of progressive equilibration with the surrounding gas before they were sequestered in the graphites. In all but one graphite, no trend was seen in the TiC size vs. distance from the graphite center, implying that appreciable TiC growth had effectively stopped before the graphites formed, or else that graphite growth was rapid compared to TiC growth. Taken together, the chemical variations among internal grains as well as the presence of partially amorphous rims and epitaxial Fe phases on some TiCs clearly indicate that the phase condensation sequence was TiC, followed by the iron phases (only found in some graphites) and finally graphite. Since graphite typically condenses at a higher temperature than iron at low pressures ( O and otherwise solar composition, the observed condensation sequence implies a relative iron enrichment in the gas or greater supersaturation of graphite relative to iron. The TEM observations allow inferences to be made about the physical conditions in the gas from which the grains condensed. Given the TiC sizes and abundances, the gas was evidently quite dusty. From the observed TiC size range of ∼20 nm to ∼500 nm (assuming ∼1 yr growth time and T ∼ 1800°K), we infer minimum Ti number densities in the gas to be ∼7 × 104 to ∼2 × 106 atoms/cc, respectively. Although the gas composition is clearly not solar, for scale, these number densities would correspond to a pressure range of ∼0.2 μbar to ∼5.0 μbar in a gas of solar composition. They also correspond to minimum TiC grain number densities of ∼3 × 10−4 to ∼0.2 grains/cc, assuming complete condensation of Ti in TiC. We estimate the maximum ratio of mean TiC grain separation distance in the gas to grain diameter from the Ti number densities as ∼3 × 105 to ∼1 × 106.

Solubility and partitioning of Ar in anorthite, diopside, forsterite, spinel, and synthetic basaltic liquids

We have investigated the solubility and partitioning of Ar in natural anorthite, diopside, forsterite, spinel, and synthetic iron-free basaltic melts. The experiments used a new technique which obviates post-quenching phase separation. Minerals and melts known to be in equilibrium are held in separate crucibles in a one bar flowing noble gas atmosphere at 1300°C or 1332°C. After a specified time the samples are quenched and the gas concentrations measured by mass spectrometry. A reversal and a rate study for Ar in anorthite indicate a close approach to equilibrium solubilities in our experiments. The solubility of Ar in the minerals is surprisingly high. In addition, the solubility of Ar in different samples of a particular mineral run in the same experiment varies more than the solubility in the same sample run in different experiments. This result suggests that noble gases are held in lattice vacancy defects. Other evidence supports defect siting: 1. (i) gases are held in very retentive sites; 2. (ii) solubility trends do not favor interstitial siting. 3. (iii) TEM imaging revealed no anomalous microstructures or dislocation densities. 4. (iv) EXAFS studies of some samples show that Kr has no preferred site in the lattices. Argon solubilities in synthetic silicate melts are lower than those observed experimentally in natural basalts. This difference correlates with the greater molar volume and polymerization of the natural basalts compared to the synthetic melts. The solubility variations greatly affect the absolute values of Ar mineral/ melt partition coefficients. Average anorthite/melt (0.6 ± 0.5) and diopside/melt (0.6 ± 0.5) partition coefficient values suggest that Ar is moderately incompatible. However, given the evidence that Ar solubility in minerals depends on lattice vacancy defect concentrations, it may not be possible to specify the partition coefficient values in a manner analogous to ionic species.

Pristine presolar silicon carbide

We report the results of a study of 81 micrometer-sized presolar SiC grains in the size range 0.5-2.6 m from the Murchison (CM2) carbonaceous chondrite. We describe a simple, nondestructive physical disaggregation technique used to isolate the grains while preserving them in their pristine state, as well as the scanning electron microscopy energy-dispersive X-ray mapping procedure used to locate them. Nine-tenths of the pristine SiCs are bounded by one or more planar surfaces consistent with cubic (3C polytype) crystal faces based on manifest symmetry elements. In addition, multiple polygonal depressions (generally 100 nm deep) are observed in more than half of these crystal faces, and these possess symmetries consistent with the structure of the 3C polytype of SiC. By comparison of these features with the surface features present on heavily etched presolar SiC grains from Murchison separate KJG, we show that the polygonal depressions on pristine grains are likely primary growth features. The etched SiCs have high densities of surface pits, in addition to polygonal depressions. If these pits are etched linear defects in the SiC, then defect densities are quite high (as much as 10 8 -10 9 /cm 2 ), about 10 3 -10 4 times higher than in typical synthetic SiCs. The polygonal depressions on crystal faces of pristine grains, as well as the high defect densities, indicate rapid formation of presolar SiC. No other primary minerals are observed to be intergrown with or overgrown on the pristine SiCs, so the presence of overgrowths of other minerals cannot be invoked to account for the survival of presolar SiC in the solar nebula. We take the absence of other primary condensates to indicate that further growth or back-reaction with the gas became kinetically inhibited as the gas-phase densities in the expanding asymptotic giant branch (AGB) stellar atmospheres (in which most of the grains condensed) became too low. However, we did observe an oxygen peak in the X-ray spectra of most pristine grains, implying silica coatings of as much as several tens of nm thickness, perhaps due to oxidation of the SiC in the solar nebula. We see little or no evidence on the pristine grains of the surface sputtering or cratering that are predicted theoretically to occur in the interstellar medium (ISM) due to supernova shocks. A possible implication is that the grains may have been protected during their residence in the ISM by surface coatings, including simple ices. Residues of such coatings may indeed be present on some pristine SiCs, because many (60%) are coated with an apparently amorphous, possibly organic phase. However, at present we do not have sufficient data on the coatings to draw secure inferences as to their nature or origin. A few irregular pristine SiCs, either fragments produced by regolith gardening on the Murchison parent body or by grain- grain collisions in the ISM, were also observed. Copyright

Adsorption of xenon and krypton on shales

Abstract Parameters for the adsorption of Xe and Kr on shales and related samples have been measured by a method that uses a mass spectrometer as a manometer. The gas partial pressures used were 10−11 atm or less; the corresponding adsorption coverages are only small fractions of a monolayer, and Henrys Law behavior is expected and observed. Heats of adsorption in the range 2–7 kcal/mol were observed. Henry constants of the order of magnitude 1 cm3 STP g−1 atm−1 at 0 to 25°C are obtained by extrapolation. Adsorption properties are variable by sample, but the general range suggests that shales might be sufficiently good adsorbents that equilibrium adsorption with modern air may account for a nontrivial fraction of the atmospheric inventory of Xe (perhaps even Kr). It seems doubtful, however, that this effect can account for the deficiency (approximately a factor of 25) of atmospheric Xe in comparison with the planetary gas patterns observed in meteorites. If gas is adsorbed on interior surfaces in shale clays and can communicate with sample exteriors only through very narrow (10−7 to 10−6 cm) channels, and thus only very slowly, equilibrium adsorption may make substantial contributions to experimentally observed ‘trapped’ gases without the need for any further trapping mechanism.

Electron energy loss spectrometry of interstellar diamonds

The results are reported of electron energy loss spectra (EELS) measurements on diamond residues from carbonaceous meteorites designed to elucidate the structure and composition of interstellar diamonds. Dynamic effective medium theory is used to model the dielectric properties of the diamonds and in particular to synthesize the observed spectra as mixtures of diamond and various pi-bonded carbons. The results are shown to be quantitatively consistent with the idea that diamonds and their surfaces are the only contributors to the electron energy loss spectra of the diamond residues and that these peculiar spectra are the result of the exceptionally small grain size and large specific surface area of the interstellar diamonds. 35 refs.