Supernova graphite in the NanoSIMS: Carbon, oxygen and titanium isotopic compositions of a spherule and its TiC sub-components

Presolar graphite spherules from the Murchison low-density separate KE3 contain a large number of internal TiC crystals that range in size from 15 to 500 nm. We have studied one such graphite grain in great detail by successive analyses with SEM, ims3f SIMS, TEM and NanoSIMS. Isotopic measurements of the ‘bulk’ particle in the ims3f indicate a supernova origin for this graphite spherule. The NanoSIMS measurements of C, N, O and Ti isotopes were performed directly on TEM ultramicrotome sections of the spherule, allowing correlated studies of the isotopic and mineralogical properties of the graphite grain and its internal crystals. We found isotopic gradients in ¹²C/¹³C and ¹⁶O/¹⁸O from the core of the graphite spherule to its perimeter, with the most anomalous compositions being present in the center. These gradients may be the result of isotopic exchange with isotopically normal material, either in the laboratory or during the particle’s history. No similar isotopic gradients were found in the ¹⁶O/¹⁷O and ¹⁴N/¹⁵N ratios, which are normal within analytical uncertainty throughout the graphite spherule. Due to an unusually high O signal, internal TiC crystals were easily located during NanoSIMS imaging measurements. It was thus possible to determine isotopic compositions of several internal TiC grains independent of the surrounding graphite matrix. These TiC crystals are significantly more anomalous in their O isotopes than the graphite, with ¹⁶O/¹⁸O ratios ranging from 14 to 250 (compared to a terrestrial value of 499). Even the most centrally located TiC grains show significant variations in their O isotopic compositions from crystal to crystal. Measurement of the Ti isotopes in three TiC grains found no variations among them and no large differences between the compositions of the different crystals and the ‘bulk’ graphite spherule. However, the same three TiC crystals vary by a factor of 3 in their ¹⁶O/¹⁸O ratios. It is not clear in what form the O is associated with the TiC grains and whether it is cogenetic or the result of surface reactions on the TiC grains before they accreted onto the growing graphite spherule. The presence of ⁴⁴Ca from short-lived ⁴⁴Ti (t_1/2 = 60y) in one of the TiC subgrains confirms the identification of this graphite spherule as a supernova condensate.     

A menagerie of graphite morphologies in the Acapulco meteorite with diverse carbon and nitrogen isotopic signatures: Implications for the evolution history of acapulcoite meteorites

Morphologies, petrographic settings and carbon and nitrogen isotopic compositions of graphites in the Acapulco meteorite, the latter determined by secondary ionization mass spectrometry, are reported. Seven different graphite morphologies were recognized, the majority of which occur enclosed exclusively in kamacite. Individual graphite grains also rarely occur in the silicate matrix. Kamacite rims surrounding taenite cores of metal grains are separated from the Ni-rich metal cores by graphite veneers. These graphite veneers impeded or prevented Ni-Fe interdiffusion during cooling. In addition, matrix FeNi metal contains considerable amounts of phosphorous (≈ 700 ppm) and silicon (≈ 300 ppm) (Pack et al., 2005 in preparation) thus indicating that results of laboratory cooling experiments in the Fe-Ni binary system are inapplicable to Acapulco metals. Graphites of different morphologies display a range of carbon and nitrogen isotopic compositions, indicating a diversity of source regions before accretion in the Acapulco parent body. The isotopic compositions point to at least three isotopic reservoirs from which the graphites originated: (1) A reservoir with heavy carbon, represented by graphite in silicates (δ¹³C = 14.3 ± 2.4 ‰ and δ¹⁵N = −103.4 ± 10.9 ‰), (2) A reservoir with isotopically light carbon and nitrogen, characteristic for the metals. Its C- and N-isotopic compositions are probably preserved in the graphite exsolutions that are isotopically light in carbon and lightest in nitrogen (δ¹³C = −17 to −23 ‰ δ¹⁵N = −141 to −159 ‰). (3) A reservoir with an assumed isotopic composition (δ¹³C ∼ −5 ‰; δ¹⁵N ∼ −50 ‰). A detailed three-dimensional tomography in reflected light microscopy of the decorations of metal-troilite spherules in the cores of orthopyroxenes and olivines and metal-troilite veins was conducted to clarify their origin. Metal and troilite veins are present only near the fusion crust. Hence, these veins are not pristine to Acapulco parent body but resulted during passage of Acapulco in Earth’s atmosphere. A thorough search for symplectite-type silicate-troilite liquid quench textures was conducted to determine the extent of closed-system partial silicate melting in Acapulco.Metal-troilite spherules in orthopyroxenes and olivines are not randomly distributed but decorate ferromagnesian silicate restite cores, indicating that the metal-spherule decoration around restite silicates took place in a silicate partial melt. Graphite inclusions in these spherules have C- and N- isotopic compositions (δ¹³C = −2.9 ± 2.5 ‰ and δ¹⁵N = −101.2 ± 32 ‰) close to the average values of graphite in metals and in the silicate matrix, thus strongly suggesting that they originated from a mixture of graphite inclusions in metals and silicate matrix graphite during a closed system crystallization process subsequent to silicate-metal-sulfide partial melting. Troilite-orthopyroxene quench symplectite textures in orthopyroxene rims are clear evidence that silicate-sulfide partial melting took place in Acapulco. Due to petrographic heterogeneity on a centimeter scale, bulk REE abundances of individual samples or of individual minerals provide only limited information and the REE abundances alone are not entirely adequate to unravel the formational processes that prevailed in the acapulcoite-lodranite parent body. The present investigations demonstrate the complexity of the evolutionary stages of acapulcoites from accretion to parent body processes.     

Condensation and mixing in supernova ejecta

Low-density graphite spherules from the Murchison carbonaceous chondrite contain TiC grains and possess excess ²⁸Si and ⁴⁴Ca (from decay of short-lived ⁴⁴Ti). These and other isotopic anomalies indicate that such grains formed by condensation from mixtures of ejecta from the interior of a core-collapse supernova with those from the exterior. Using homogenized chemical and isotopic model compositions of the eight main burning zones as end-members, Travaglio et al. (1999) attempted to find mixtures whose isotopic compositions match those observed in the graphite spherules, subject to the condition that the atomic C/O ratio = 1. They were partially successful, but this chemical condition does not guarantee condensation of TiC at a higher temperature than graphite, which is indicated by the spherule textures. In the present work, model compositions of relatively thin layers of ejecta within the main burning zones computed by Rauscher et al. (2002) for Type II supernovae of 15, 21 and 25 M_? are used to construct mixtures whose chemical compositions cause equilibrium condensation of TiC at a higher temperature than graphite in an attempt to match the textures and isotopic compositions of the spherules simultaneously. The variation of pressure with temperature and the change in elemental abundances with time due to radioactive decay were taken into account in the condensation calculations. Layers were found within the main Ni, O/Ne, He/C and He/N zones that, when mixed together, simultaneously match the carbon, nitrogen and oxygen isotopic compositions, ⁴⁴Ti/⁴⁸Ti ratios and inferred initial ²⁶Al/²⁷Al ratios of the low-density graphite spherules, even at subsolar ¹²C/¹³C ratios. Due to the relatively large proportion of material from the Ni zone and the relative amounts of the two layers of the Ni zone required to meet these conditions, predicted ²⁸Si excesses are larger than observed in the low-density graphite spherules, and large negative δ⁴⁶Ti/⁴⁸Ti, δ⁴⁷Ti/⁴⁸Ti, δ⁴⁹Ti/⁴⁸Ti and δ⁵⁰Ti/⁴⁸Ti are produced, in contrast to the observed normal δ⁴⁶Ti/⁴⁸Ti and δ⁴⁷Ti/⁴⁸Ti, large positive δ⁴⁹Ti/⁴⁸Ti and smaller positive δ⁵⁰Ti/⁴⁸Ti. Although better matches to the observed δ⁴⁶Ti/⁴⁸Ti, δ⁴⁷Ti/⁴⁸Ti and ²⁸Si excesses can be found using much smaller amounts of Ni zone material and some Si/S zone material, it is very difficult to match simultaneously the Ti and Si isotopic compositions in any mixtures of material from these deep layers with He/C and He/N zone material, regardless of the condensation sequence. The occurrence of Fe-rich, Si-poor metal grains inside the graphite spherules does not have a satisfactory explanation.     

Oxygen deficient Ti oxides (natural magnéli phases) from mudstone xenoliths with native iron from Disko,central West Greenland

Mudstone xenoliths in a strongly reduced andesitic subaquatic breccia with native iron from the Asuk Member on Disko contain Ti oxides which are oxygen deficient relative to rutile. Ore microscopy reveals that the mudstone xenoliths contain former clastic oxide grains which have equilibrated to blue Ti oxides and grey aluminous Ti oxides. They also contain still immature coal fragments in a glassy matrix with native iron.The blue oxides are compositionally similar to magnéli phases Ti_nO_2n–1 within the range n=4 to 7, and several grains contain more than one natural magnéli phase. Two other phases found are 1) pale orange blebs in magnéli phases with a composition approaching Al₁Ti ₁ ³⁺ Ti ₂ ⁴⁺ O₇ (AlTi phase B) and 2) grey oxide rims on magnéli phases or independent grains of the compositional series Al_2–x(Ti _0.5 ⁴⁺ (Mg,Fe)_0.5)_xTi _n–2 ⁴⁺ O_2n–1 with n mostly between 7 and 10 (AlTi phase A). The natural magnéli phases equilibrated at oxygen fugacities 4 to 5 log units below the Fe-W oxygen buffer at igneous temperatures and represent the most reduced high-temperature environment yet recorded among native iron bearing rocks from Disko. The extremely reducing conditions were met in rocks where coal fragments were still in a state of degassing hydrocarbon components at the time of quenching. Field geology and carbon barometry indicate equilibration at pressures of less than 10 bars.     

Chemical and oxygen isotopic compositions of accretionary rim and matrix olivine in CV chondrites: Constraints on the evolution of nebular dust

A correlation of petrography, mineral chemistry and in situ oxygen isotopic compositions of fine-grained olivine from the matrix and of fine- and coarse-grained olivine from accretionary rims around Ca-Al-rich inclusions (CAIs) and chondrules in CV chondrites is used here to constrain the processes that occurred in the solar nebula and on the CV parent asteroid. The accretionary rims around Leoville, Vigarano, and Allende CAIs exhibit a layered structure: the inner layer consists of coarse-grained, forsteritic and ¹⁶O-rich olivine (Fa_1-40 and Δ¹⁷O = −24‰ to −5‰; the higher values are always found in the outer part of the layer and only in the most porous meteorites), whereas the middle and the outer layers contain finer-grained olivines that are more fayalitic and ¹⁶O-depleted (Fa_15-50 and Δ¹⁷O = −18‰ to +1‰). The CV matrices and accretionary rims around chondrules have olivine grains of textures, chemical and isotopic compositions similar to those in the outer layers of accretionary rims around CAIs. There is a correlation between local sample porosity and olivine chemical and isotopic compositions: the more compact regions (the inner accretionary rim layer) have the most MgO- and ¹⁶O-rich compositions, whereas the more porous regions (outer rim layers around CAIs, accretionary rims around chondrules, and matrices) have the most MgO- and ¹⁶O-poor compositions. In addition, there is a negative correlation of olivine grain size with fayalite contents and Δ¹⁷O values. However, not all fine-grained olivines are FeO-rich and ¹⁶O-poor; some small (<1 μm in Leoville and 5-10 μm in Vigarano and Allende) ferrous (Fa_>20) olivine grains in the outer layers of the CAI accretionary rims and in the matrix show significant enrichments in ¹⁶O (Δ¹⁷O = −20‰ to −10‰). We infer that the inner layer of the accretionary rims around CAIs and, at least, some olivine grains in the finer portions of accretionary rims and CV matrices formed in an ¹⁶O-rich gaseous reservoir, probably in the CAI-forming region. Grains in the outer layers of the CAI accretionary rims and in the rims around chondrules as well as matrix may have also originated as ¹⁶O-rich olivine. However, these olivines must have exchanged O isotopes to variable extents in the presence of an ¹⁶O-poor reservoir, possibly the nebular gas in the chondrule-forming region(s) and/or fluids in the parent body. The observed trend in isotopic compositions may arise from mixtures of ¹⁶O-rich forsterites with grain overgrowths or newly formed grains of ¹⁶O-poor fayalitic olivines formed during parent body metamorphism. However, the observed correlations of chemical and isotopic compositions of olivine with grain size and local porosity of the host meteorite suggest that olivine accreted as a single population of ¹⁶O-rich forsterite and subsequently exchanged Fe-Mg and O isotopes in situ in the presence of aqueous solutions (i.e., fluid-assisted thermal metamorphism).     

Metal and associated phases in Bishunpur,a highly unequilibrated ordinary chondrite

It appears that the highly unequilibrated Bishunpur ordinary chondrite preserves phase relations acquired during solar nebular processes to a relatively high degree; metamorphic temperatures may not have exceeded 300–350°C. The major categories of metal are: 3 kinds of metal in the metal matrix, three kinds in chondrule interiors and 2 kinds in chondrule rims. The fine-grained matrix metal is highly variable in composition: the kamacite Co content (7.8 ± 2.0 mg/g) is within the L-group range (6.7–8.2 mg/g) but extends well above and below; its Ni content (38 ± 5 mg/g) is considerably lower than in more equilibrated chondrites and taenite is Ni-rich ( > 450 mg/g) and unzoned. These compositions imply equilibration at very low temperatures of about 300–350°C. It seems unlikely that volume diffusion could account for the observed relatively unzoned phases; a better model involves mass transport by grain boundary diffusion and grain growth at the indicated temperatures. We find no evidence that the matrix was ever at higher temperatures. Large (50–650 μm) polycrystalline metal aggregates consisting of individually zoned crystals are also found in the matrix; they probably represent clusters formed in the solar nebula. A few large (50–250 μm) round monocrystalline grains are also present in the matrix.Metal-bearing chondrules tend to be highly reduced; they contain low-Ni metal that occasionally contains Si and/or Cr. Silicates in these chondrules tend to have low $\text{FeO}\text{(FeO + MgO)}$ ratios. The Si-rich metal grains are never in contact with silicates and are always surrounded by troilite with a poorly characterized Ca, Cr-sulfide at the metal-troilite interface; they appear to be high temperature nebular condensates that avoided oxidation even during the chondrule forming process. Silicon contents drop below our detection limit when the sulfide coating is absent. Much more common in chondrule interiors are Si-free spheroidal metal grains not associated with sulfides. These have Ni and Co contents very similar to the Si-bearing grains, and appear to be oxidized variants of the same material. The third class of chondrule metal is fine ( ~1 μm) dusty grains inside individual olivine grains. These seem to reflect high temperature in situ reduction of FeO from the olivine.The composition of kamacite is different in sulfide-rich and sulfide-poor chondrule rims and in both cases it is dissimilar to the compositions in the chondrule interiors and matrix; this indicates that chondrule rims could not have resulted from reactions with the matrix, but are primary features acquired prior to accretton.     

NanoSIMS isotopic analysis of small presolar grains: Search for Si3N4 grains from AGB stars and Al and Ti isotopic compositions of rare presolar SiC grains

We report isotopic ratio measurements of small SiC and Si₃N₄ grains, with special emphasis on presolar SiC grains of type Z, and new nucleosynthesis models for ²⁶Al/²⁷Al and the Ti isotopic ratios in asymptotic giant branch (AGB) stars. With the NanoSIMS we analyzed 310 SiC grains from Murchison (carbonaceous CM2 chondrite) separate KJB (diameters 0.25-0.45 μm) and 153 SiC grains from KJG (diameters 1.8-3.7 μm), 154 SiC and 23 Si₃N₄ grains from Indarch (enstatite EH4 chondrite) separate IH6 (diameters 0.25-0.65 μm) for their C and N isotopic compositions, 549 SiC and 142 Si₃N₄ grains from IH6 for their C and Si isotopic compositions, 13 SiC grains from Murchison and 66 from Indarch for their Al-Mg compositions, and eight SiC grains from Murchison and 10 from Indarch for their Ti isotopic compositions. One of the original objectives of this effort was to compare isotopic analyses with the NanoSIMS with analyses previously obtained with the Cameca IMS 3f ion microprobe. Many of the Si₃N₄ grains from Indarch have isotopic anomalies but most of these apparently originate from adjacent SiC grains. Only one Si₃N₄ grain, with ¹³C and ¹⁴N excesses, has a likely AGB origin. The C, N, and Si isotopic data show that the percentage of SiC grains of type Y and Z increase with decreasing grain size (from ∼1% for grains >2 μm to ∼5-7% for grains of 0.5 μm), providing an opportunity for isotopic analyses in these rare grains. Our measurements expand the number of Al-Mg analyses on SiC Z grains from 4 to 23 and the number of Ti analyses on Z grains from 2 to 11. Inferred²⁶Al/²⁷Al ratios of Z grains are in the range found in mainstream and Y grains and do not exceed those predicted by models of AGB nucleosynthesis. Cool bottom processing (CBP) has been invoked to explain the low ¹²C/¹³C ratios of Z grains, but this process apparently does not lead to increased ²⁶Al production in the parent stars of these grains. This finding is in contrast to presolar oxide grains where CBP is needed to explain their high ²⁶Al/²⁷Al ratios. The low ^46,47,49Ti/⁴⁸Ti ratios found in Z grains and their correlation with low ²⁹Si/²⁸Si ratios extend the trend seen in mainstream grains and confirm an origin in low-metallicity AGB stars. The relatively large excesses in ³⁰Si and ⁵⁰Ti in Z grains are predicted by our models to be the result of increased production of these isotopes by neutron-capture nucleosynthesis in low-metallicity AGB stars. However, the predicted excesses in ⁵⁰Ti (and ⁴⁹Ti) are much larger than those found. Even lowering the strength of the ¹³C pocket cannot solve this discrepancy in a consistent way.     

Graves Nunataks 95209: A snapshot of metal segregation and core formation

GRA 95209 may provide our best opportunity to date to understand the earliest stages of core formation in asteroidal bodies. This lodranite preserves a physically, chemically, and mineralogically complex set of metal-sulfide veins. High-resolution X-ray computed tomography revealed three distinct lithologies. The dominant mixed metal-silicate-sulfide matrix is cut by metal-rich, graphite-bearing veins exceeding 1 cm in width and grades into a volumetrically minor metal-poor region. Silicate compositions and modal abundances are typical for lodranites, while the mineralogy of the metal-sulfide component is complex and differs among the three lithologies. Kamacite and troilite occur with chromite, tetrataenite, schreibersite, graphite, and a range of phosphates. An ³⁹Ar-⁴⁰Ar age of 4.521 ± 0.006 Ga measures the time of closure of the K-Ar system. Carbon rosettes within the metal-rich vein are nitrogen-poor, well crystallized, include kamacite sub-grains of composition comparable to the host metal, and are essentially isotopically homogeneous (δ¹³C ∼ −33‰). In contrast, carbon rosettes within metal of the metal-poor lithology are N-poor, poorly crystallized, include kamacite grains that are Ni-poor compared to their host metal, and are isotopically heterogeneous (δ¹³C ranging from −50 to +80‰) even within a single metal grain. The silicate portion of GRA 95209 is similar to the lodranite EET 84302, sharing a common texture, silicate mineral compositions, and Ar-Ar age. GRA 95209 and EET 84302 are intermediate between acapulcoites and lodranites. Both experienced Fe,Ni-FeS melting with extensive melt migration, but record only the onset of silicate partial melting with limited migration of silicate melt. The complex metal-sulfide veins in GRA 95209 resulted from low-degree partial melting and melt migration and intruded the matrix lithology. Reactions between solid minerals and melt, including oxidation-reduction reactions, produced the array of phosphates, schreibersite, and tetrataenite. Extensive reduction in the metal-rich vein resulted from its origin in a hotter portion of the asteroid. This difference in thermal history is supported by the graphite structures and isotopic compositions. The graphite rosettes in the metal-rich vein are consistent with high-temperature igneous processing. In contrast, the carbon in the metal-poor lithology appears to preserve a record of formation in the nebula prior to parent-body formation. Carbon incorporated from the solar nebula into a differentiating asteroid is preferentially incorporated in metal-sulfide melts that form a core, but does not achieve isotopic homogeneity until extensive thermal processing occurs.     

A NanoSIMS study of Si- and Ca-Ti-isotopic compositions of presolar silicon carbide grains from supernovae

We report results from NanoSIMS isotopic measurements on 37 presolar silicon carbide grains of type X which are believed to have formed in the ejecta of supernova explosions. Isotopic data were obtained for Si and Ca-Ti (all grains), C and N (two grains), and Ti (one grain). All X grains exhibit large enrichments in ²⁸Si (up to 5× solar), in agreement with previously studied X grains. On a scale of 200 nm, the Si-isotopic ratios do not vary by more than the analytical uncertainties of several percent in all but one X grain. This implies that most X grains formed from well-mixed regions in supernova ejecta. X grain M9-68-3 is characterized by two regions with distinct Si- and Ti-isotopic signatures which may either represent two distinct grains or overgrowth of matter from two different mixtures in the supernova ejecta. Most of the Ca in the X grains is most likely contamination as indicated by close to normal ⁴²Ca/⁴⁰Ca ratios. Seven X grains show enhanced ⁴⁴Ca/⁴⁰Ca ratios of up to 6× the solar ratio. Spatial distributions of ⁴⁴Ca excesses and Ti are positively correlated, giving strong support to the view that excesses in ⁴⁴Ca are due to the decay of radioactive ⁴⁴Ti. Inferred initial ⁴⁴Ti/⁴⁸Ti ratios are between 0.01 and 0.28 and are correlated with Si-isotopic ratios. Radiogenic ⁴⁴Ca is widely distributed in six X grains. X grain M9-132-4 exhibits a pronounced heterogeneity in the distribution of radiogenic ⁴⁴Ca and ⁴⁸Ti as well as in ⁴⁴Ti/⁴⁸Ti, pointing to presence of a small Ti-rich subgrain or heterogeneous loss of Ca and Ti after grain formation. This grain has a unique Si-isotopic composition with ³⁰Si/²⁹Si = 2.2× the solar ratio and C- and N-isotopic compositions as typically observed in X grains.     

Diffusion of trace elements in FeNi metal: Application to zoned metal grains in chondrites

We have measured diffusion coefficients for P, Cr, Co, Ni, Cu, Ga, Ge, Ru, Pd, Ir, and Au in Fe metal from 1150 to 1400°C and at 1 bar and 10 kbar. Diffusion couples were prepared from high-purity Fe metal and metal from the IIA iron meteorite Coahuila (single crystal kamacite) or the pallasite Springwater (polycrystalline kamacite) and held at run conditions for 3.5 to 123 h. Diffusion profiles were measured using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) or the electron microprobe. Many elements were measured from the same experimental runs so interelemental comparisons are improved over other data sets in which data for different elements come from different experiments. Some literature diffusion coefficients (D) for Ni and Co in taenite can be up to a factor of 3 higher for Ni than Co, yet our results show no difference (e.g., D_Ni and D_Co ∼ 2.2 × 10^-15 m²/s at 1150°C). Thus, diffusion of Ni and Co in single crystal taenite will not measurably fractionate the Ni/Co ratio. On the other hand, the large difference in D_Ni and D_Ir (D_Ir is ∼5 times lower) and the similarity of D_Ni and D_Ru at all temperatures investigated indicates that Ni/Ir and Ni/Ru ratios in zoned metal grains will be useful discriminators of processes controlled by diffusion vs. volatility. In zoned metal grains in primitive chondrites, deviations of the Ni/Ru and Ni/Ir ratios from a condensation curve are opposite to a diffusion-controlled process, but consistent with a volatility-controlled process. The new multielement diffusion coefficients will also be useful in evaluating a variety of other processes in planetary science.     

Volatilization kinetics of silicon carbide in reducing gases: an experimental study with applications to the survival of presolar grains in the solar nebula

The volatilization kinetics of single crystal α-SiC, polycrystalline β-SiC, and SiO₂ (cristobalite or glass) were determined in H₂-CO₂, CO-CO₂, and H₂-CO-CO₂ gas mixtures at oxygen fugacities between 1 log unit above and 10 log units below the iron-wüstite (IW) buffer and temperatures in the range 1151 to 1501°C. Detailed sets of experiments on SiC were conducted at 2.8 and 6.0 log units below IW (IW-2.8 and IW-6.0) at a variety of temperatures, and at 1300°C at a variety of oxygen fugacities. Transmission electron microscopic and Rutherford backscattering spectroscopic characterization of run products shows that the surface of SiC exposed to IW-2.8 is characterized by a thin (<1 μm thick), continuous layer of cristobalite. SiC exposed to IW-6.0 lacks such a layer (or its thickness is <0.01 μm), although some SiO₂ was found within pits and along incised grain boundaries.In H₂-CO₂ gas mixtures above ∼IW-3, the similarity of the SiC volatilization rate and of its dependence on temperature and fO₂ to that for SiO₂ suggests that SiC volatilization is controlled by volatilization of a SiO₂ layer that forms on the surface of the SiC. With decreasing log fO₂ from ∼IW-3 to ∼IW-6, the SiC volatilization rate is constant at constant temperature, whereas that for SiO₂ increases. The independence of the SiC volatilization rate from the gas composition under these conditions suggests that the rate-controlling step is a solid-solid reaction at the internal SiC/SiO₂ interface. For gas compositions more reducing than ∼IW-6, the SiC volatilization rate increases with decreasing fO₂, with both bare SiC surfaces and perhaps silica residing in pits and along incised grain boundaries contributing to the overall reaction rate.If the volatilization mechanism and reaction rate in the solar nebula were the same as in our H₂-CO₂ experiments at IW-6.0, then estimated lifetimes of 1-μm-diameter presolar SiC grains range from several thousand years at ∼900°C, to ∼1 yr at 1100°C, ∼1 d at 1300°C, and ∼1 h at 1400°C. The corresponding lifetimes for 10-μm SiC grains would be an order of magnitude longer. If the supply of oxidants to surfaces of presolar SiC grains were rate limiting—for example, at T > 1100°C for P^tot= 10⁻⁶ atm and sticking coefficient = 0.01, then the calculated lifetimes would be about 10 yr for 10-μm-diameter grains, essentially independent of temperature. The results thus imply that presolar SiC grains would survive short heating events associated with formation of chondrules (minutes) and calcium-, aluminum-rich inclusions (days), but would have been destroyed by exposure to hot (≥900°C) nebular gases in less than several thousand years unless they were coated with minerals inert to reaction with a nebular gas.     

Petrologic study of SJ101, a new forsterite-bearing CAI from the Allende CV3 chondrite

The forsterite-bearing Type B (FoB) CAI SJ101 consists of three major structural units: (1) light patches of sector-zoned, poikilitic Al-rich clinopyroxene (Cpx) with numerous inclusions of small spinel grains and aggregates and subordinate amounts of Mg-rich melilite (Mel) and anorthite (An) (Sp-Cpx lithology), (2) dark sinuous bands of Al-rich clinopyroxene with large (up to ∼300 × 60 μm) poikilitically enclosed euhedral forsterite (Fo) crystals (Fo-Cpx lithology), and (3) the external Cpx-Sp-An rim overlying the entire inclusion. The two major lithologies are always separated by a transition zone of clinopyroxene poikilitically enclosing both forsterite and spinel. The patches of the Sp-Cpx lithology exhibit significant textural and mineralogical variability that is size-dependent. Small patches typically consist of Cpx and spinel with minor remnants of melilite and/or its alteration products. Large patches contain Mel-An-rich cores with either equigranular-ophitic-subophitic or ‘lacy’ textures reminiscent of those in Types B or C CAIs, respectively. All silicates poikilitically enclose numerous spinel grains of identical habit. Both melilite and anorthite gradually disappear toward the boundary with the Fo-Cpx lithology. Neither the evaporation mantle of Al-rich melilite typical of other FoBs nor the Wark-Lovering rim is present. Secondary minerals include grossular, monticellite, magnetite, and a few grains of wollastonite, andradite, and nepheline.Being a rather typical FoB mineralogically and chemically, texturally SJ101 differs from other FoBs in displaying the nearly complete segregation of forsterite from spinel which occur only in the Fo-Cpx and Sp-Cpx lithologies, respectively. The complex, convoluted internal structure of SJ101 suggests that the coarse-grained Sp-An-Mel-Cpx cores and Fo-Cpx lithology represent the precursor materials of FoBs, proto-CAIs and Fo-rich accretionary rims. While the inferred chemistry and mineralogy of the Fo-rich rims are fairly typical, the high Åk content in SJ101 melilite (78.7-82.3 mol.%) implies that the SJ101 proto-CAIs represent a new type of CAIs that has not been sampled before. This type of CAIs might have formed by remelting of spinel-rich condensates.The Group II REE pattern, slightly negative δ²⁹Si and δ²⁵Mg values, and nearly solar ratios of the major elements in the bulk SJ101 suggest that its precursors, proto-CAIs and Fo-rich rims, could have formed by a non-equilibrium condensation in a closed system of solar composition somewhat depleted in a super-refractory evaporation residue. The proposed formation scenario of SJ101 invokes a non-steady cooling and condensation of the nebular gas interrupted by at least two distinct melting episodes required to account for the igneous textures of the Mel-An-Cpx-rich cores (proto-CAIs) and the Fo-Cpx lithology.     

Composition,nucleation, and growth of iron oxide concretions

Iron oxide concretions are formed from post depositional, paleogroundwater chemical interaction with iron minerals in porous sedimentary rocks. The concretions record a history of iron mobilization and precipitation caused by changes in pH, oxidation conditions, and activity of bacteria. Transport limited growth rates may be used to estimate the duration of fluid flow events. The Jurassic Navajo Sandstone, an important hydrocarbon reservoir and aquifer on the Colorado Plateau, USA, is an ideal stratum to study concretions because it is widely distributed, well exposed and is the host for a variety of iron oxide concretions.Many of the concretions are nearly spherical and some consist of a rind of goethite that nearly completely fills the sandstone porosity and surrounds a central sandstone core. The interior and exterior host-rock sandstones are similar in detrital minerals, but kaolinite and interstratified illite–smectite are less abundant in the interior. Lepidocrocite is present as sand-grain rims in the exterior sandstone, but not present in the interior of the concretions.Widespread sandstone bleaching resulted from dissolution of early diagenetic hematite grain coatings by chemically reducing water that gained access to the sandstone through fault conduits. The iron was transported in solution and precipitated as iron oxide concretions by oxidation and increasing pH. Iron diffusion and advection growth time models place limits on minimum duration of the diagenetic, fluid flow events that formed the concretions. Concretion rinds 2 mm thick and 25 mm in radius would take place in 2000 years from transport by diffusion and advection and in 3600 years if transport was by diffusion only. Solid concretions 10 mm in radius would grow in 3800 years by diffusion or 2800 years with diffusion and advection.Goethite (α-FeO (OH)) and lepidocrocite (γ-FeO (OH)) nucleated on K-feldspar grains, on illite coatings on sand grains, and on pore-filling illite, but not on clean quartz grains. Model results show that regions of detrital K-feldspar in the sandstone that consume H⁺ more rapidly than diffusion to the reaction site determine concretion size, and spacing is related to diffusion and advection rates of supply of reactants Fe²⁺, O₂, and H⁺.     

U and Th zonation in apatite observed by laser ablation ICPMS, and implications for the (U-Th)/He system

A laser-ablation inductively-coupled plasma mass spectrometry technique was developed to measure U, Th, and Ce zonation in polished sections of apatite for assessing the consequences of parent zonation for (U-Th)/He thermochronometry. The technique produces concentration maps with an averaging length-scale of ∼20 μm, comparable to the α-stopping distance, and a precision of ∼5% down to few ppm concentration levels. A model was developed to transform the measured concentration distribution into a simplified representation for use in spherical-geometry He production-diffusion models. To illustrate these methods, 30 sections of apatite from a single granite (GC863) were mapped. Every analyzed apatite from GC863 is zoned, with most grains having variable thickness rims and terminations that are enriched in U and Th by about a factor of three over the grain cores.Parent zonation has three independent effects on (U-Th)/He He ages: it influences the α ejection correction, the ⁴He concentration profile which governs diffusive loss, and, via radiation damage trap accumulation, spatial variability of diffusivity within the crystal. If the observed zonation is typical of the apatite population in GC863, use of the standard homogenous α ejection correction would cause He ages to be on average 3% too young, and with a large amount of grain-to-grain variability (9% too young in the most rim-enriched case to 6% too old in a core-enriched case). Independent of the ejection correction, the concentration profile modifies the effective closure temperature of the apatites by placing more (or less) ⁴He near the grain edge. The parent zonation in GC863 apatites causes closure temperatures to range from four degrees lower (rim-enriched case) to two degrees higher (core-enriched case) than applies in the homogenous case. Alpha ejection and concentration profile effects on He age are additive and of the same sense. In the case of typical grains in GC863 cooled between 1 and 10 °C/Ma, the two effects are roughly equal in magnitude. The effects of intracrystalline variations in radiation damage trap accumulation become apparent at slow cooling rates (1 °C/Ma). For example, in rim-enriched GC863 grains cooled at 1 °C/Ma, preferential accumulation of radiation damage traps near the grain rim almost compensates for the higher loss rate expected of ⁴He also located preferentially near the rim. Under some circumstances strong rim-enrichment may actually increase the effective closure temperature of an apatite. Zonation at the level observed in GC863 modifies the ⁴He/³He spectra substantially from that expected from a uniform distribution. Measured ⁴He/³He spectra are strikingly similar to predictions based on the mapped eU distributions of the very same crystals, supporting the overall validity of the analytical and interpretive approach presented here.The magnitude and style of U, Th zonation documented in GC863 is one possible source of frequently observed over-dispersion of apatite (U-Th)/He ages as well as anomalous ⁴He/³He spectra.     

Origin and thermometry of graphites from Itapecerica supracrustal succession of the southern Sao Francisco Craton by C isotopes,X-ray diffraction,and Raman spectroscopy

ABSTRACT

In the mines of the Nacional de Grafite Company around Itapecerica (Minas Gerais), located in the southern Sao Francisco Craton, occurs a supracrustal succession of high-grade metamorphic rocks including quartzite, garnet-biotite gneiss, and graphite schist formed in the Palaeoproterozoic (2.0 Ga). During metamorphic processes, organic matter was progressively transformed into graphite. From four graphite samples of three different mines (two samples from high-grade metamorphic graphite schist and two generated by hydrothermal recrystallization of the graphite schist), the origin and formation temperature of this mineral was obtained by C isotopes, X-ray diffraction (XRD), and Raman spectroscopy. The values of δ¹³C range between ?21.23 and ?27.89 ‰, indicating that the source of the graphite was a primitive biogenic carbon material. High-grade metamorphic graphites show average temperatures around 729°C, while hydrothermal recrystallizated graphites (vein-graphites) show temperatures around 611°C by XRD, which correspond to granulite- to amphibolite facies conditions. The hydrothermal process with percolation of C-O-H fluids leads to a decrease in the crystal size along stacking direction (Lc₍₀₀₂₎) when compared with the previously formed high-grade metamorphism graphites. An update of the current tectonic model about the collisional process during Rhyacian-Orosirian orogeny in the Sao Francisco Craton is proposed to insert the formation of the Itapecerica graphite-rich metasedimentary sequence.     

Mass-dependent fractionation of Mg, Si, and Fe isotopes in five stony cosmic spherules

We have measured with an electron microprobe the Mg, Al, Si, Ca, Ti, Mn, and Fe contents of five strongly heated stony cosmic spherules (sCS) from the South Pole water well. We have also measured the isotopic compositions of Si, and when possible of Mg and of Fe in these objects by ion microprobe. Except for iron, the measured elemental compositions are chondritic within a factor of 2. In four samples, the ratio of ⁵⁷Fe/⁵⁶Fe exceeds the terrestrial value by 3.5‰ to 48‰. Mass-dependent fractionation of the isotopes of Si ranges from ∼2 to ∼8 ‰/AMU in three samples. Mg is clearly fractionated in only one sample, for which δ²⁵Mg = ∼8 ‰. The extent of mass-dependent fractionation of the isotopes and, by implication, of evaporative loss generally follows a trend Mg < Si < Fe. The trend is similar to that found in laboratory heating experiments of charges with solar composition. Although the observed isotopic inhomogeneities within some samples call into question the strict validity of the Rayleigh equation for the sCS, its approximate application to our new and to previously published results for Mg suggests that evaporative losses of greater than 40 wt.% occur rarely from sCS, and that the precursor grains of the sCS had a CM-carbonaceous-chondrite-like complement of Mg, Si, Ca, and Al. Low Fe contents relative to CM abundances could reflect an unusual precursor composition, or, more probably, losses by processes that did not fractionate isotopes, i.e., ejection of immiscible FeS and FeNi beads from the melt or rapid, complete separation and decomposition of FeS at the surface.     

Smyer H-chondrite impact-melt breccia and evidence for sulfur vaporization

Smyer is an H-chondrite impact-melt breccia containing ∼20 vol% 0.5- to 13-mm-thick silicate-rich melt veins surrounding unmelted subrounded chondritic clasts up to 7 cm in maximum dimension. At the interface between some of the melt veins and chondritic clasts, there are troilite-rich regions consisting of unmelted, crushed 0.2- to 140-μm-size angular silicate grains and chondrule fragments surrounded by troilite and transected by thin troilite veins. Troilite fills every available fracture in the silicates, including some as thin as 0.1 μm. Little metallic Fe-Ni is present in these regions: the FeS/Fe modal ratio ranges from ∼25:1 to ∼500:1, far higher than the eutectic weight ratio of 7.5:1. The texture of these regions indicates that the sulfide formed from a fluid of very low viscosity. The moderately high viscosity (0.2 poise) and large surface tension of liquid FeS, its inability to wet silicate grain surfaces at low oxygen fugacities, and the supereutectic FeS/Fe ratios in the troilite-rich regions indicate that the fluid was a vapor. It seems likely that during the shock event that melted Smyer, many silicates adjacent to the melt veins were crushed. Upon release of shock pressure, some of the troilite evaporated and dissociated. Molecules of S₂ were transported and condensed into fractures and around tiny silicate grains; there, they combined with Fe from small adjacent metallic Fe-Ni grains to form troilite. The Ni content at the edges of some of these metal grains increased significantly; Co from these Ni-rich grains diffused into nearby kamacite. Impact-induced S volatilization may have played a major role in depleting the surface of 433 Eros (and other chondritic asteroids) in S.     

Chemical evolution of metal in refractory inclusions in CV3 chondrites

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure distributions of the siderophile elements V, Fe, Co, Ni, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in Fremdlinge with a spatial resolution of 15 to 25 μm. A sulfide vein in a refractory inclusion in Allende (CV3-oxidized) is enriched in Rh, Ru, and Os with no detectable Pd, Re, Ir, or Pt, indicating that Rh, Ru, and Os were redistributed by sulfidation of the inclusion, causing fractionation of Re/Os and other siderophile element ratios in Allende CAIs. Fremdlinge in compact Type-A inclusions from Efremovka (CV3-reduced) exhibit subsolidus exsolution into kamacite and taenite and minimal secondary formation of V-magnetite and schreibersite. Siderophile element partitioning between taenite and kamacite is similar to that observed previously in iron meteorites, while preferential incorporation of the light PGEs (Ru, Rh, Pd) relative to Re, Os, Ir, and Pt by schreibersite was observed. Fremdling EM2 (CAI Ef2) has an outer rim of P-free metal that preserves the PGE signature of schreibersite, indicating that EM2 originally had a phosphide rim and lost P to the surrounding inclusion during secondary processing. Most Fremdlinge have chondrite-normalized refractory PGE patterns that are unfractionated, with PGE abundances derived from a small range of condensation temperatures, ∼1480 to 1468 K at P_tot = 10⁻³ bar. Some Fremdlinge from the same CAI exhibit sloping PGE abundance patterns and Re/Os ratios up to 2 × CI that likely represent mixing of grains that condensed at various temperatures.     

Lithium isotopic systematics of peridotite xenoliths from Hannuoba, North China Craton: Implications for melt-rock interaction in the considerably thinned lithospheric mantle

Li concentrations and isotopic compositions of coexisting minerals (ol, opx, and cpx) from peridotite xenoliths entrained in the Hannuoba Tertiary basalts, North China Craton, provide insight into Li isotopic fractionation between mantle minerals during melt-rock interaction in the considerably thinned lithospheric mantle. Bulk analyses of mineral separates show significant enrichment of Li in cpx (2.4-3.6 ppm) relative to olivine (1.2-1.8 ppm), indicating that these peridotites have been affected by mantle metasomatism with mafic silicate melts. Bulk olivine separates (δ⁷Li ∼ +3.3‰ to +6.4‰) are isotopically heavier than coexisting pyroxenes (δ⁷Li ∼ −3.3‰ to −8.2‰ in cpx, and −4.0‰ to −6.7‰ in opx). Such large variation suggests Li elemental and isotopic disequilibrium. This conclusion is supported by results from in situ SIMS analyses of mineral grains where significant Li elemental and isotopic zonations exist. The olivine and opx have lower Li concentrations and heavier Li isotopes in the rims than in the cores. This reverse correlation of δ⁷Li with Li concentrations indicates diffusive fractionation of Li isotopes. However, the zoning patterns in coexisting cpx show isotopically heavier rims with higher Li abundances. This positive correlation between δ⁷Li and Li concentrations suggests a melt mixing trend. We attribute Li concentration and isotope zonation in minerals to the effects of two-stage diffusive fractionation coupled with melt-rock interaction. The earliest melts may have been derived from the subducted oceanic slab with low δ⁷Li values produced by isotopic fractionation during the dehydration of the seawater-altered slab. Melts at later stages were derived from the asthenosphere and interacted with the peridotites, producing the Li elemental and isotopic zoning in mineral grains. These data thus provide evidence for multiple-stage peridotite-melt interaction in the lithospheric mantle beneath the northern North China Craton.     

A major revision of iron meteorite cooling rates—An experimental study of the growth of the Widmanstätten pattern

In this study kamacite was experimentally grown in taenite grains of Fe-Ni-P alloys containing between 5 and 10 wt% Ni and 0 and 1.0 wt% P. Both isothermal heat treatments and non-isothermal heat treatments at cooling rates of 2 to 5°C/day were carried out. Analytical electron microscopy was used to examine the orientation and chemical composition of the kamacite and the surrounding taenite matrix. The kamacite so produced is spindle or rod shaped and has a Widmanstätten pattern orientation. The presence of heterogeneous sites such as phosphides is necessary for the nucleation of the intergranular kamacite. During kamacite growth both Ni and P partition between kamacite and taenite with chemical equilibrium at the two phase interface. The growth kinetics are limited by the diffusion of Ni in taenite. Additional diffusion experiments showed that the volume diffusion coefficient of Ni in taenite is raised by a factor of 10 at 750°C in the presence of only 0.15 wt% P.A numerical model to simulate the growth of kamacite in Fe-Ni-P alloys, based on our experimental results, was developed and applied to estimate the cooling rates of the iron meteorites. The cooling rates predicted by the new model are two orders of magnitude greater than those of previous studies. For example the cooling rates of chemical groups I, IIIAB and IVA are 400–4000°C/10⁶years, 150–1400°C/ 10⁶ years and 750–6000°C/10⁶years respectively. Previous models gave 1–4°C/10⁶ years, 1–10°C/10⁶ years and 3–200°C/10⁶ years. Such fast cooling rates can be interpreted to indicate that meteorite parent bodies need only be a few kilometers in diameter or that iron meteorites can be formed near the surface of larger asteroidal bodies.