Frank J. Stadermann

Synthesis and Solid-State NMR Structural Characterization of 13C-Labeled Graphite Oxide

The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13–labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.

Mineralogy and Petrology of Comet 81P/Wild 2 Nucleus Samples

The bulk of the comet 81P/Wild 2 (hereafter Wild 2) samples returned to Earth by the Stardust spacecraft appear to be weakly constructed mixtures of nanometer-scale grains, with occasional much larger (over 1 micrometer) ferromagnesian silicates, Fe-Ni sulfides, Fe-Ni metal, and accessory phases. The very wide range of olivine and low-Ca pyroxene compositions in comet Wild 2 requires a wide range of formation conditions, probably reflecting very different formation locations in the protoplanetary disk. The restricted compositional ranges of Fe-Ni sulfides, the wide range for silicates, and the absence of hydrous phases indicate that comet Wild 2 experienced little or no aqueous alteration. Less abundant Wild 2 materials include a refractory particle, whose presence appears to require radial transport in the early protoplanetary disk.

Organics captured from comet 81P/Wild 2 by the Stardust spacecraft

Organics found in comet 81P/Wild 2 samples show a heterogeneous and unequilibrated distribution in abundance and composition. Some organics are similar, but not identical, to those in interplanetary dust particles and carbonaceous meteorites. A class of aromatic-poor organic material is also present. The organics are rich in oxygen and nitrogen compared with meteoritic organics. Aromatic compounds are present, but the samples tend to be relatively poorer in aromatics than are meteorites and interplanetary dust particles. The presence of deuterium and nitrogen-15 excesses suggest that some organics have an interstellar/protostellar heritage. Although the variable extent of modification of these materials by impact capture is not yet fully constrained, a diverse suite of organic compounds is present and identifiable within the returned samples.

Isotopic Compositions of Cometary Matter Returned by Stardust

Hydrogen, carbon, nitrogen, and oxygen isotopic compositions are heterogeneous among comet 81P/Wild 2 particle fragments; however, extreme isotopic anomalies are rare, indicating that the comet is not a pristine aggregate of presolar materials. Nonterrestrial nitrogen and neon isotope ratios suggest that indigenous organic matter and highly volatile materials were successfully collected. Except for a single 17O-enriched circumstellar stardust grain, silicate and oxide minerals have oxygen isotopic compositions consistent with solar system origin. One refractory grain is 16O-enriched, like refractory inclusions in meteorites, suggesting that Wild 2 contains material formed at high temperature in the inner solar system and transported to the Kuiper belt before comet accretion.

Impact Features on Stardust: Implications for Comet 81P/Wild 2 Dust

Particles emanating from comet 81P/Wild 2 collided with the Stardust spacecraft at 6.1 kilometers per second, producing hypervelocity impact features on the collector surfaces that were returned to Earth. The morphologies of these surprisingly diverse features were created by particles varying from dense mineral grains to loosely bound, polymineralic aggregates ranging from tens of nanometers to hundreds of micrometers in size. The cumulative size distribution of Wild 2 dust is shallower than that of comet Halley, yet steeper than that of comet Grigg-Skjellerup.

Elemental compositions of comet 81P/Wild 2 samples collected by Stardust

We measured the elemental compositions of material from 23 particles in aerogel and from residue in seven craters in aluminum foil that was collected during passage of the Stardust spacecraft through the coma of comet 81P/Wild 2. These particles are chemically heterogeneous at the largest size scale analyzed (∼180 ng). The mean elemental composition of this Wild 2 material is consistent with the CI meteorite composition, which is thought to represent the bulk composition of the solar system, for the elements Mg, Si, Mn, Fe, and Ni to 35%, and for Ca and Ti to 60%. The elements Cu, Zn, and Ga appear enriched in this Wild 2 material, which suggests that the CI meteorites may not represent the solar system composition for these moderately volatile minor elements.

Infrared Spectroscopy of Comet 81P/Wild 2 Samples Returned by Stardust

Infrared spectra of material captured from comet 81P/Wild 2 by the Stardust spacecraft reveal indigenous aliphatic hydrocarbons similar to those in interplanetary dust particles thought to be derived from comets, but with longer chain lengths than those observed in the diffuse interstellar medium. Similarly, the Stardust samples contain abundant amorphous silicates in addition to crystalline silicates such as olivine and pyroxene. The presence of crystalline silicates in Wild 2 is consistent with mixing of solar system and interstellar matter. No hydrous silicates or carbonate minerals were detected, which suggests a lack of aqueous processing of Wild 2 dust.

Aluminum-, calcium- and titanium-rich oxide stardust in ordinary chondrite meteorites

We report O-, Al-Mg-, K-, Ca-, and Ti-isotopic data for a total of 96 presolar oxide grains found in residues of several unequilibrated ordinary chondrite meteorites. Identified grain types include Al2O3 ,M gAl2O4, hibonite (CaAl12O19), and Ti oxide. This work greatly increases the presolar hibonite database, and is the first report of presolarTioxide.O-isotopiccompositionsof thegrainsspanpreviouslyobservedrangesandindicateanoriginin red giant and asymptotic giant branch (AGB) stars of low mass (<2.5 M� ) for most grains. Cool bottom processing in the parent AGB stars is required to explain isotopic compositions of many grains. Potassium-41 enrichments in hibonite grains are attributable to in situ decay of now-extinct 41 Ca. Inferred initial 41 Ca/ 40 Ca ratios are in good agreement with model predictionsfor low-mass AGB star envelopes,provided that ionizationsuppresses 41 Cadecay. Stable Mg and Ca isotopic ratios of most of the hibonite grains reflect primarily the initial compositions of the parent starsandaregenerallyconsistentwithexpectationsforGalacticchemicalevolution,butrequiresomelocalinterstellar chemical inhomogeneity. Very high 17 O/ 16 Oo r 25 Mg/ 24 Mg ratios suggest an origin for some grains in binary star systemswheremasstransferfromanevolvedcompanionhasalteredtheparentstarcompositions.Asupernovaorigin for the hitherto enigmatic 18 O-rich Group 4 grains is strongly supported by multielement isotopic data for two grains. The Group 4 data are consistent with an origin in a single supernova in which variable amounts of material from the deep 16 O-rich interior mixed with a unique end-member mixture of the outer layers. The Ti oxide grains primarily formed in low-mass AGB stars. They are smaller and rarer than presolar Al2O3, reflecting the lower abundance of Ti than Al in AGB envelopes. Subject headingg dust, extinction — Galaxy: evolution — nuclear reactions, nucleosynthesis, abundances — stars: AGB and post-AGB — supernovae: general

Characterization of Presolar Silicate and Oxide Grains in Primitive Carbonaceous Chondrites

Raster ion imaging of the oxygen isotopes with the NanoSIMS ion microprobe has been used to identify presolar grains in two primitive meteorites. Eleven presolar silicates and eight presolar oxides were identified in the primitive carbonaceous chondrite Acfer 094 for abundances of 325 and 360 parts per million (ppm), respectively. In addition, nine presolar silicates and five presolar oxide grains were identified in the CO3 chondrite ALHA 77307, for abundancesof 320and200ppm,respectively.Theseabundances,whicharematrix-normalizedandcorrectedforinstrumental detectionefficiencies,aremuchhigherthanthoseofotherpresolarphases,withtheexceptionof nanodiamonds,although the latter may not all be presolar. The chemical compositions of six presolar silicate grains from ALHA 77307 were elucidated by Auger spectroscopy. Transmission electron microscopy (TEM) analysis of one presolar silicate grain revealed a nonstoichiometric composition and an amorphous structure as indicated by the diffuse electron diffraction pattern. The oxygen isotopic compositions of the presolar silicates indicate origins in red giant and asymptotic giant branch stars. Analysis of the Si isotopic compositions of 10 presolar silicates provides further constraints on the effects of Galactic chemical evolution. Subject headingg circumstellar matter — dust, extinction — Galaxy: evolution — nuclear reactions, nucleosynthesis, abundances — stars: evolution

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.