Rhodium, gold and other highly siderophile element abundances in chondritic meteorites

The abundances of the highly siderophile elements (HSE) Re, Os, Ir, Ru, Pt, Rh, Pd and Au, and ¹⁸⁷Os/¹⁸⁸Os isotope ratios have been determined for a set of carbonaceous, ordinary, enstatite and Rumuruti chondrites, using an analytical technique that permits the precise and accurate measurement of all HSE from the same digestion aliquot. Concentrations of Re, Os, Ir, Ru, Pt and Pd were determined by isotope dilution ICP-MS and N-TIMS analysis. The monoisotopic elements Rh and Au were quantified relative to the abundance of Ir.Differences in HSE abundances and ratios such as Re/Os, ¹⁸⁷Os/¹⁸⁸Os, Pd/Ir and Au/Ir between different chondrite classes are further substantiated with new data, and additional Rh and Au data, including new data for CI chondrites. Systematically different relative abundances of Rh between different chondrite classes are reminiscent of the behaviour of Re. Carbonaceous chondrites are characterized by low average Rh/Ir of 0.27 ± 0.03 (1s) which is about 20% lower than the ratio for ordinary (0.34 ± 0.02) and enstatite chondrites (EH: 0.33 ± 0.01; EL: 0.32 ± 0.01). R chondrites show higher and somewhat variable Rh/Ir of 0.37 ± 0.07.Well-defined linear correlations of HSE, in particular for bulk samples of ordinary and EL chondrites, are explained by binary mixing and/or dilution by silicates. The HSE carriers responsible for these correlations have a uniform chemical composition, indicating efficient homogenization of local nebular heterogeneities during or prior to the formation of the host minerals in chondrite components. Excepting Rumuruti chondrites and Au in carbonaceous chondrites, these correlations also suggest that metamorphism, alteration and igneous processes had negligible influence on the HSE distribution on the bulk sample scale.Depletion patterns for Rh, Pd and Au in carbonaceous chondrites other than CI are smoothly related to condensation temperatures and therefore consistent with the general depletion of moderately volatile elements in carbonaceous chondrites. Fractionated HSE abundance patterns of ordinary, enstatite and Rumuruti chondrites, however, are more difficult to explain. Fractional condensation combined with the removal of metal phases at various times, and later mixing of early and late formed metal phases may provide a viable explanation. Planetary fractionation processes that may have affected precursor material of chondrite components cannot explain the HSE abundance patterns of chondrite groups. HSE abundances of some, but not all Rumuruti chondrites may be consistent with solid sulphide-liquid sulphide fractionation processes during impact induced melting.     

Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from CR2 carbonaceous chondrites

We report both oxygen- and magnesium-isotope compositions measured in situ using a Cameca ims-1280 ion microprobe in 20 of 166 CAIs identified in 47 polished sections of 15 CR2 (Renazzo-type) carbonaceous chondrites. Two additional CAIs were measured for oxygen isotopes only. Most CR2 CAIs are mineralogically pristine; only few contain secondary phyllosilicates, sodalite, and carbonates - most likely products of aqueous alteration on the CR2 chondrite parent asteroid. Spinel, hibonite, grossite, anorthite, and melilite in 18 CAIs have ¹⁶O-rich (Δ¹⁷O = −23.3 ± 1.9‰, 2σ error) compositions and show no evidence for postcrystallization isotopic exchange commonly observed in CAIs from metamorphosed CV carbonaceous chondrites. The inferred initial ²⁶Al/²⁷Al ratios, (²⁶Al/²⁷Al)₀, in 15 of 16 ¹⁶O-rich CAIs measured are consistent with the canonical value of (4.5-5) × 10⁻⁵ and a short duration (<0.5 My) of CAI formation. These data do not support the “supra-canonical” values of (²⁶Al/²⁷Al)₀ [(5.85-7) × 10⁻⁵] inferred from whole-rock and mineral isochrons of the CV CAIs. A hibonite-grossite-rich CAI El Djouf 001 MK #5 has uniformly ¹⁶O-rich (Δ¹⁷O = −23.0 ± 1.7‰) composition, but shows a deficit of ²⁶Mg and no evidence for ²⁶Al. Because this inclusion is ¹⁶O-rich, like CAIs with the canonical (²⁶Al/²⁷Al)₀, we infer that it probably formed early, like typical CAIs, but from precursors with slightly nonsolar magnesium and lower-than-canonical ²⁶Al abundance. Another ¹⁶O-enriched (Δ¹⁷O = −20.3 ± 1.2‰) inclusion, a spinel-melilite CAI fragment Gao-Guenie (b) #3, has highly-fractionated oxygen- and magnesium-isotope compositions (∼11 and 23‰/amu, respectively), a deficit of ²⁶Mg, and a relatively low (²⁶Al/²⁷Al)₀ = (2.0 ± 1.7) × 10⁻⁵. This could be the first FUN (Fractionation and Unidentified Nuclear effects) CAI found in CR2 chondrites. Because this inclusion is slightly ¹⁶O-depleted compared to most CR2 CAIs and has lower than the canonical (²⁶Al/²⁷Al)₀, it may have experienced multistage formation from precursors with nonsolar magnesium-isotope composition and recorded evolution of oxygen-isotope composition in the early solar nebula over  My. Eight of the 166 CR2 CAIs identified are associated with chondrule materials, indicating that they experienced late-stage, incomplete melting during chondrule formation. Three of these CAIs show large variations in oxygen-isotope compositions (Δ¹⁷O ranges from −23.5‰ to −1.7‰), suggesting dilution by ¹⁶O-depleted chondrule material and possibly exchange with an ¹⁶O-poor (Δ¹⁷O > −5‰) nebular gas. The low inferred (²⁶Al/²⁷Al)₀ ratios of these CAIs (<0.7 × 10⁻⁵) indicate melting >2 My after crystallization of CAIs with the canonical (²⁶Al/²⁷Al)₀ and suggest evolution of the oxygen-isotope composition of the inner solar nebula on a similar or a shorter timescale. Because CAIs in CR2 and CV chondrites appear to have originated in a similarly ¹⁶O-rich reservoir and only a small number of CR2 and CV CAIs were affected by chondrule melting events in an ¹⁶O-poor gaseous reservoir, the commonly observed oxygen-isotope heterogeneity in CAIs from metamorphosed CV chondrites is most likely due to fluid-solid isotope exchange on the CV asteroidal body rather than gas-melt exchange. This conclusion does not preclude that some CV CAIs experienced oxygen-isotope exchange during remelting, instead it implies that such remelting is unlikely to be the dominant process responsible for oxygen-isotope heterogeneity in CV CAIs. The mineralogy, oxygen and magnesium-isotope compositions of CAIs in CR2 chondrites are different from those in the metal-rich, CH and CB carbonaceous chondrites, providing no justification for grouping CR, CH and CB chondrites into the CR clan.     

Petrological investigation of the Ganyu peridotite in the Sulu ultrahigh-pressure terrane, eastern China

The ultramafic body sampled in the Chinese Continental Scientific Drilling (CCSD) Hole PP3 is located in the eastern part of the Dabie-Sulu UHP metamorphic belt near Donghai County. It is about 480 m thick, and consists chiefly of garnet peridotite, dunite and serpentinite. The principal minerals include olivine, chromium spinel, diopside, enstatite, garnet with minor secondary augite, phlogopite and amphibole. Both the olivine and orthopyroxene are highly magnesian, and the garnet is pyropic with 5.4-6.4% CaO and 0.3-3.3% Cr₂O₃. Two generations of clinopyroxene are present; an early diopside followed by augite. Chromium spinels are highly variable with Cr#s (100Cr / (Cr + Al)) between 51 and 89, and their compositions reflect different processes of formation, namely partial melting and eclogite, amphibole and greenschist facies metamorphism. The Mg#s (100 Mg / (Mg + Fe²⁺))of the spinels correlate positively with the Cr#s but negatively with oxygen fugacity. Based on the spinel compositions the ultramafic rocks originated in the shallow mantle, then subducted to depths of more than 100 km and finally exhumed to the surface. They underwent partial melting at shallow depths, mostly in the spinel facies, and were later transformed into garnet peridotites during deep subduction. All of the rocks were weakly metasomatized during exhumation and were subjected to retrograde metamorphism.     

CO2 solubility in Martian basalts and Martian atmospheric evolution

To understand possible volcanogenic fluxes of CO₂ to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO₂ solubility. CO₂ contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe³⁺/Fe^T was measured by Mössbauer spectroscopy. The CO₂ contents of glasses show no dependence on Fe³⁺/Fe^T and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO₂ contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol⁻¹ cm⁻² for the integrated area under the carbonate doublet at 1430 and 1520 cm⁻¹. The experimentally determined CO₂ solubilities allow calibration of the thermodynamic parameters governing dissolution of CO₂ vapor as carbonate in silicate melt, K_II, (Stolper and Holloway, 1988) as follows: , ΔV⁰ = 20.85 ± 0.91 cm³ mol⁻¹, and ΔH⁰ = −17.96 ± 10.2 kJ mol⁻¹. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO₂ dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and f_O2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO₂ contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO₂ at IW and 0.24 wt.% of CO₂ at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO₂ to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO₂ to an early Martian greenhouse is plausible.     

The oxygen-isotope composition of chondrules and isolated forsterite and olivine grains from the Tagish Lake carbonaceous chondrite

The oxygen-isotope compositions (obtained by laser fluorination) of hand-picked separates of isolated forsterite, isolated olivine and chondrules from the Tagish Lake carbonaceous chondrite describe a line (δ¹⁷O = 0.95 * δ¹⁸O − 3.24; R² = 0.99) similar to the trend known for chondrules from other carbonaceous chondrites. The isolated forsterite grains (Fo_99.6-99.8; δ¹⁸O = −7.2‰ to −5.5‰; δ¹⁷O = −9.6‰ to −8.2‰) are more ¹⁶O-rich than the isolated olivine grains (Fo_39.6-86.8; δ¹⁸O = 3.1‰ to 5.1‰; δ¹⁷O = −0.3‰ to 2.2‰), and have chemical and isotopic characteristics typical of refractory forsterite. Chondrules contain olivine (Fo_97.2-99.8) with oxygen-isotope compositions (δ¹⁸O = −5.2‰ to 5.9‰; δ¹⁷O = −8.1‰ to 1.2‰) that overlap those of isolated forsterite and isolated olivine. An inverse relationship exists between the Δ¹⁷O values and Fo contents of Tagish Lake isolated forsterite and chondrules; the chondrules likely underwent greater exchange with ¹⁶O-poor nebular gases than the forsterite. The oxygen-isotope compositions of the isolated olivine grains describe a trend with a steeper slope (1.1 ± 0.1, R² = 0.94) than the carbonaceous chondrite anhydrous mineral line (CCAM_slope = 0.95). The isolated olivine may have crystallized from an evolving melt that exchanged with ¹⁶O-poor gases of somewhat different composition than those which affected the chondrules and isolated forsterite. The primordial components of the Tagish Lake meteorite formed under conditions similar to other carbonaceous chondrite meteorite groups, especially CMs. Its alteration history has its closest affinities to CI carbonaceous chondrites.     

Deuterium enrichments in chondritic macromolecular material—Implications for the origin and evolution of organics, water and asteroids

Here we report the elemental and isotopic compositions of the insoluble organic material (IOM) isolated from several previously unanalyzed meteorites, as well as the reanalyses of H isotopic compositions of some previously measured samples (Alexander et al., 2007). The IOM in ordinary chondrites (OCs) has very large D enrichments that increase with increasing metamorphism and decreasing H/C, the most extreme δD value measured being almost 12,000‰. We propose that such large isotopic fractionations could be produced in the OC parent bodies through the loss of isotopically very light H₂ generated when Fe was oxidized by water at low temperatures (<200 °C). We suggest that similar isotopic fractionations were not generated in the IOM of CV and CO chondrites with similar metamorphic grades and IOM H/C ratios because proportionately less water was consumed during metamorphism, and the remaining water buffered the H isotopic composition of the IOM even a H was being lost from it.Hydrogen would also have been generated during the alteration of CI, CM and CR carbonaceous chondrites. The IOM in these meteorites exhibit a considerable range in isotopic compositions, but all are enriched in D, as well as ¹⁵N, relative to terrestrial values. We explore whether these enrichments could also have been produced by the loss of H₂, but conclude that the most isotopically anomalous IOM compositions in meteorites from these groups are probably closest to their primordial values. The less isotopically anomalous IOM has probably been modified by parent body processes. The response of IOM to these processes was complex and varied, presumably reflecting differences in conditions within and between parent bodies.The D enrichments associated with H₂ generation, along with exchange between D-rich IOM and water in the parent bodies, means that it is unlikely that any chondrites retain the primordial H isotopic composition of the water ice that they accreted. The H isotopic compositions of the most water-rich chondrites, the CMs and CIs, are probably the least modified and their compositions (δD ? −25‰) suggest that their water did not form at large radial distances from the Sun where ice is predicted to be very D-rich. Yet models to explain the O isotopic composition of inner Solar System bodies require that large amounts of ice were transported from the outer to the inner Solar System.     

The formation and alteration of the Renazzo-like carbonaceous chondrites I: Implications of bulk-oxygen isotopic composition

To better understand the role of aqueous alteration on the CR chondrite parent asteroid, a whole-rock oxygen isotopic study of 20 meteorites classified as Renazzo-like carbonaceous chondrites (CR) was conducted. The CR chondrites analyzed for their oxygen isotopes were Dhofar 1432, Elephant Moraine (EET) 87770, EET 92042, EET 96259, Gao-Guenie (b), Graves Nunataks (GRA) 95229, GRA 06100, Grosvenor Mountains (GRO) 95577, GRO 03116, LaPaz Ice Field (LAP) 02342, LAP 04720, Meteorite Hills (MET) 00426, North West Africa (NWA) 801, Pecora Escarpment (PCA) 91082, Queen Alexandra Range (QUE) 94603, QUE 99177, and Yamato-793495 (Y-793495). Three of the meteorites, Asuka-881595 (A-881595), GRA 98025, and MET 01017, were found not to be CR chondrites. The remaining samples concur petrographically and with the well-established oxygen-isotope mixing line for the CR chondrites. Their position along this mixing line is controlled both by the primary oxygen-isotopic composition of their individual components and their relative degree of aqueous alteration. Combined with literature data and that of this study, we recommend the slope for the CR-mixing line to be 0.70 ± 0.04 (2σ), with a δ¹⁷O-intercept of −2.23 ± 0.14 (2σ).Thin sections of Al Rais, Shi?r 033, Renazzo, and all but 3 samples analyzed for oxygen isotopes were studied petrographically. The abundance of individual components is heterogeneous among the CR chondrites, but FeO-poor chondrules and matrix are the most abundant constituents and therefore, dominate the whole-rock isotopic composition. The potential accreted ice abundance, physico-chemical conditions of aqueous alteration (e.g. temperature and composition of the fluid) and its duration control the degree of alteration of individual CR chondrites. Combined with literature data, we suggest that LAP 02342 was exposed to lower temperature fluid during alteration than GRA 95229. With only two falls, terrestrial alteration of the CR chondrites complicates the interpretation of their whole rock isotopic composition, particularly in the most aqueously altered samples, and those with relatively higher matrix abundances. We report that QUE 99177 is the isotopically lightest whole rock CR chondrite known (δ¹⁸O = −2.29‰, δ¹⁷O = −4.08‰), possibly due to isotopically light unaltered matrix; which shows that the anhydrous component of the CR chondrites is isotopically lighter than previously thought. Although it experienced aqueous alteration, QUE 99177 provides the best approximation of the pristine CR-chondrite parent body’s oxygen-isotopic composition, before aqueous alteration took place. Using this value as a new upper limit on the anhydrous component of the CR chondrites, water/rock ratios were recalculated and found to be higher than previously thought; ratios now range from 0.281 to 1.157. We also find that, according to their oxygen isotopes, a large number of CR chondrites appear to be minimally aqueously altered; although sample heterogeneity complicates this interpretation.     

The Rumuruti chondrite group

Since 1994, the Rumuruti (R) chondrites have been recognized as a new, well-established chondrite group differing from carbonaceous, ordinary, and enstatite chondrites. The first R chondrite, Carlisle Lakes, was found in Australia in 1977. Meanwhile, the number has increased to 107 (December, 2010). This group is named after the Rumuruti meteorite, the first and so far the only R chondrite fall. Most of the R chondrites are breccias containing a variety of different clasts embedded in a clastic matrix. Some textural and mineralogical characteristics can be summarized as follows: (a) the chondrule abundance in large fragments and in unbrecciated rocks is ∼35–50 vol%; (b) Ca,Al-rich inclusions are rare; (c) the olivine abundance is typically 65–78 vol%; (d) the mean chondrule diameter is ∼400 μm; (e) in unequilibrated R chondrites, low-Ca pyroxene is dominating, whereas in equilibrated R chondrites it is Ca-rich pyroxene; (f) the typical olivine in a metamorphosed lithology is ∼Fa_38–40; (g) matrix olivine in unequilibrated, type 3 fragments and rocks has much higher Fa (∼45–60 mol%) compared to matrix olivines in type 4–6 lithologies (∼Fa_38–41); (h) spinels have a high TiO₂ of ∼5 wt%; (i) abundant different noble metal-bearing phases (metals, sulfides, tellurides, arsenides) occur. The exception is the metamorphosed, type 5/6 R chondrite La Paz Icefield 04840 which contains hornblende, phlogopite, and Ca-poor pyroxene, the latter phase typically occurring in low-grade metamorphosed R chondrites only.In bulk composition, R chondrites have some affinity to ordinary chondrites: (a) the absence of significant depletions in Mn and Na in R chondrites and ordinary chondrites is an important feature to distinguish these groups from carbonaceous chondrites; (b) total Fe (∼24 wt%) of R chondrites is between those of H and L chondrites (27.1 and 21.6 wt%, respectively); (c) the average CI/Mg-normalized lithophile element abundances are ∼0.95 × CI, which is lower than those for carbonaceous chondrites (≥1.0 × CI) and slightly higher than those for ordinary chondrites (∼0.9 × CI); (d) trace element concentrations such as Zn (∼150 ppm) and Se (∼15 ppm) are much higher than in ordinary chondrites; (e) the whole rock Δ¹⁷O of ∼2.7 for R chondrites is the highest among all meteorite groups, and the mean oxygen isotope composition is δ¹⁷O = 5.36 ± 0.43, δ¹⁸O = 5.07 ± 0.86, Δ¹⁷O = +2.72 ± 0.31; (f) noble gas cosmic ray exposure ages of R chondrites range between ∼0.1 and ∼70 Ma. More than half of the R chondrites analyzed for noble gases contain implanted solar wind and, thus, are regolith breccias. The 43 R chondrites from Northern Africa analyzed so far for noble gases seem to represent at least 16 falls. Although the data base is still scarce, the data hint at a major collision event on the R chondrite parent body between 15 and 25 Ma ago.     

Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from Rumuruti (R) chondrites

We report oxygen- and magnesium-isotope compositions of Ca,Al-rich inclusions (CAIs) from several Rumuruti (R) chondrites measured in situ using a Cameca ims-1280 ion microprobe. On a three-isotope oxygen diagram, δ¹⁷O vs. δ¹⁸O, compositions of individual minerals in most R CAIs analyzed fall along a slope-1 line. Based on the variations of Δ¹⁷O values (Δ¹⁷O = δ¹⁷O − 0.52 × δ¹⁸O) within individual inclusions, the R CAIs are divided into (i) ¹⁶O-rich (Δ¹⁷O ∼ −23-26‰), (ii) uniformly ¹⁶O-depleted (Δ¹⁷O ∼ −2‰), and (iii) isotopically heterogeneous (Δ¹⁷O ranges from −25‰ to +5‰). One of the hibonite-rich CAIs, H030/L, has an intermediate Δ¹⁷O value of −12‰ and a highly fractionated composition (δ¹⁸O ∼ +47‰). We infer that like most CAIs in other chondrite groups, the R CAIs formed in an ¹⁶O-rich gaseous reservoir. The uniformly ¹⁶O-depleted and isotopically heterogeneous CAIs subsequently experienced oxygen-isotope exchange during remelting in an ¹⁶O-depleted nebular gas, possibly during R chondrite chondrule formation, and/or during fluid-assisted thermal metamorphism on the R chondrite parent asteroid.Three hibonite-bearing CAIs and one spinel-plagioclase-rich inclusion were analyzed for magnesium-isotope compositions. The CAI with the highly fractionated oxygen isotopes, H030/L, shows a resolvable excess of ²⁶Mg (²⁶Mg^∗) corresponding to an initial ²⁶Al/²⁷Al ratio of ∼7 × 10⁻⁷. Three other CAIs show no resolvable excess of ²⁶Mg (²⁶Mg^∗). The absence of ²⁶Mg^∗ in the spinel-plagioclase-rich CAI from a metamorphosed R chondrite NWA 753 (R3.9) could have resulted from metamorphic resetting. Two other hibonite-bearing CAIs occur in the R chondrites (NWA 1476 and NWA 2446), which appear to have experienced only minor degrees of thermal metamorphism. These inclusions could have formed from precursors with lower than canonical ²⁶Al/²⁷Al ratio.     

Composition of matrix in the CR chondrite LAP 02342

We report evidence of interchondrule matrix heterogeneity on a scale of ∼50 μm in the well-preserved CR2 chondrite LAP 02342. Despite minor effects resulting from asteroidal aqueous alteration, the matrix in this CR chondrite seems to preserve much of the compositional record of nebular fines. We carried out electron-microprobe studies using a 3-μm-diameter beam; we analyzed 10 elements in 36- or 49-point grids on 11 ca. 50 × 50-μm rectangular areas of matrix. Each grid area has a distinct composition, inconsistent with a simple model of matrix material having a uniform composition throughout the nebular formation region of the CR chondrites. On S-Fe, Mg-Si, K-Na and K-Al scatter diagrams, the grid areas (i.e., different matrix patches) are largely separated from each other; plots of means with 95% confidence limits demonstrate that the compositions are resolvable. Five matrix areas were analyzed again in duplicate runs; excellent agreement was observed between duplicate studies. LAP 02342 experienced two forms of mild aqueous alteration - as patchy enrichments in Ca (inferred to reflect CaCO₃) and as regions in which sulfide laths are embedded within phyllosilicates. Despite this evidence of aqueous transport, the effect on the composition of matrix is not resolvable. For example, matrix points that were adjacent to points with high CaCO₃ contents show elemental concentrations similar to those in regions having only one or two points with a Ca enrichment. It appears that secondary minerals are found in areas where there are suitable precursor phases and voids into which new phases could grow unimpeded. Calcium appears to be unique in forming a phase that greatly lowers the Ca⁺⁺ content of the aqueous medium, thus enhancing the rate of diffusion. Because chondrules vary widely in bulk composition, the formation of chondrules in small sets (100 or less) could generate “smoke” and mesostasis spray with compositions unique to each set. However, if these nanoparticles were moving independently in the nebula, it would not have been possible to have preserved compositional variations. We therefore infer that the anomalous materials were preserved in small nebular structures, probably as porous chondrules formed by low degrees of melting.     

A single asteroidal source for extraterrestrial Ordovician chromite grains from Sweden and China: High-precision oxygen three-isotope SIMS analysis

We examined oxygen three-isotope ratios of 48 extraterrestrial chromite (EC) grains extracted from mid-Ordovician sediments from two different locations in Sweden, and one location in south-central China. The ages of the sediments (∼470 Ma) coincide with the breakup event of the L chondrite parent asteroid. Elemental compositions of the chromite grains are generally consistent with their origin from L or LL chondrite parent bodies. The average Δ¹⁷O (‰-deviation from the terrestrial mass-fractionation line, measured in situ from 15 μm spots by secondary ion mass spectrometry; SIMS) of EC grains extracted from fossil meteorites from Thorsberg and Brunflo are 1.17 ± 0.09‰ (2σ) and 1.25 ± 0.16‰, respectively, and those of fossil micrometeorites from Thorsberg and Puxi River are 1.10 ± 0.09‰, and 1.11 ± 0.12‰, respectively. Within uncertainty these values are all the same and consistent with the L chondrite group average Δ¹⁷O = 1.07 ± 0.18‰, but also with the LL chondrite group average Δ¹⁷O = 1.26 ± 0.24‰ (Clayton et al., 1991). We conclude that the studied EC grains from correlated sediments from Sweden and China are related, and most likely originated in the same event, the L chondrite parent body breakup. We also analyzed chromites of modern H, L and LL chondrites and show that their Δ¹⁷O values coincide with averages of Δ¹⁷O of bulk analyses of H, L and LL chondrites. This study demonstrates that in situ oxygen isotope data measured by SIMS are accurate and precise if carefully standardized, and can be used to classify individual extraterrestrial chromite grains found in sediments.     

Zirconolite,allanite and hoegbomite in a marble skarn from the Bergell contact aureole: implications for mobility of Ti,Zr and REE

Zirconolite, allanite and hoegbomite are present as accessory phases in a metasomatically altered spinel-calcite-marble from the contact with the Bergell intrusives (Switzerland/Italy). Textural relationships indicate a step-wise alteration of spinel to 1) hoegbomite or corundum + magnetite, 2) margarite and 3) chlorite. Replacement of spinel by hoegbomite can be described by the substitution 1.94(Mg²⁺, Fe²⁺, Zn²⁺, Mn²⁺, Ca²⁺)Ti⁴⁺ +0.12(OH^–) where Al³⁺ and Fe³⁺ are held constant. The average composition of the Bergell hoegbomites is given by the formula Fe _0.97 ²⁺ Mg_0.69Zn_0.04Ti_0.17Al_3.94Fe _0.06 ³⁺ O_7.98(OH)_0.02 and seems to be imposed by the composition of pre-existing spinel. During the first two steps of spinel alteration, calcite was replaced by anorthite+phlogopite, and the rare earth element(REE)-bearing minerals zirconolite, allanite and sphene were formed. Allanites have characteristic chondrite-normalized REE patterns with enrichment in the light REE. The zirconolite patterns show a marked increase in concentration from La to Ce, followed by an almost constant section. Sphene lacks detectable La, and its REE patterns vary from grain to grain. Contemporaneous formation of phlogopite, REE-bearing minerals and hoegbomite during replacement of the spinel-calcite-marble indicates that the metamorphic fluid introduced potassium along with REE and other high valence cations (Ti⁴⁺, Zr⁴⁺, U⁴⁺, Th^4A3804265, Nb^5A3804265, Y^3A3804265) possibly as polynuclear complexes. The abundance of fluorine-bearing phlogopite and fluor-apatite as well as their close association with REE-bearing minerals and hoegbomite suggests F^– and PO ₄ ^3– as likely ligands for complexing of the above mentioned elements.     

Dissolution rates of phyllosilicates as a function of bacterial metabolic diversity

Weathering experiments using biotite and phlogopite in the presence of bacteria were conducted to better understand biotic dissolution kinetics and processes (proton- and ligand-promoted dissolution) under aerobic conditions. Miniature batch reactors (300 μl in microplate wells) were used at 24 °C for 3 days with and without bacterial strains. Abiotic experiments were performed with organic and nitric acids in order to calibrate the biotite-phlogopite chemical dissolution. An empirical model was used to fit the pH dependence for iron release rate (r_Fe) considering the influence of both protons and ligands from acidic to neutral conditions (pH ranging from 3 to 7): r_Fe=k_H(a_H+)^m+k_L(a_L)¹ where k is the apparent rate constant, a_H+ and a_L are the activities of protons and ligands, and m and l are the reaction orders. For both minerals in most cases at a given pH, the iron release rates in the presence of bacteria were in good agreement with rates determined by the chemical model and could be explained by a combination of proton- and ligand-promoted processes. Bacteria affect mineral dissolution and iron release rates through the quantities and nature of the organic acids they produce. Three domains were differentiated and proposed as biochemical models of mica dissolution: (1) below pH 3, only proton-promoted dissolution occurred, (2) in weakly acidic solutions both ligand- and proton-promoted mechanisms were involved, and (3) iron immobilization occured, at pH values greater than 4 for biotite and greater than 5 for phlogopite. This model allows us to distinguish the “weathering pattern phenotypes” of strains. Bacteria that are isolated from horizons poor in carbon appear more efficient at weathering micas than bacterial strains isolated from environments rich in carbon. Moreover, our results suggest that the mineral could exert a control on the release of organic acids and the “weathering pattern phenotypes” of bacteria.     

Kinetics of biotite dissolution and Fe behavior under low O2 conditions and their implications for Precambrian weathering

Biotite dissolution experiments were carried out to better understand the dissolution kinetics and Fe behavior under low O₂ conditions, and to give an insight into the Precambrian weathering. Mineral dissolution with a continuous flow-through reactor was employed at 25 °C for up to 65 days varying partial pressure of atmospheric oxygen (PO₂), pH (6.86 and 3.01) and Fe content in mineral (1.06 and 0.11 mol of Fe per O₁₀(OH,F)₂ for biotite and phlogopite, respectively) independently for the examination of their effects on biotite dissolution. Low PO₂ conditions were achieved in a newly developed glove box (PO₂ ? 6 × 10⁻⁴ atm; referred to as anoxic conditions), which was compared to the present, ambient air conditions (0.2 atm of PO₂; oxic conditions). The biotite dissolution rate was slightly faster under anoxic conditions at pH 6.86 while it was not affected by PO₂ at pH 3.01. There was no direct effect of Fe content on dissolution rate at pH 6.86 while there was a small difference in dissolution rate between biotite and phlogopite at pH 3.01. The 1.5 order-of-magnitude faster release rate of Fe under anoxic conditions for biotite dissolution at pH 6.86 resulted from the difference in ratio of Fe³⁺ precipitates remaining in the reactor to Fe dissolved (about 60% and 100% under anoxic and oxic conditions, respectively), which is caused mainly by the difference in PO₂. The results infer that the Fe²⁺ and Fe³⁺ contents in the Paleoproterozoic paleosols, fossil weathering profiles, are reflected by atmospheric oxygen levels at the time of weathering.     

Oxygen isotopic compositions of chondrules from the metal-rich chondrites Isheyevo (CH/CBb), MAC 02675 (CBb) and QUE 94627 (CBb)

It has been recently suggested that (1) CH chondrites and the CB_b/CH-like chondrite Isheyevo contain two populations of chondrules formed by different processes: (i) magnesian non-porphyritic (cryptocrystalline and barred) chondrules, which are similar to those in the CB chondrites and formed in an impact-generated plume of melt and gas resulted from large-scale asteroidal collision, and (ii) porphyritic chondrules formed by melting of solid precursors in the solar nebula. (2) Porphyritic chondrules in Isheyevo and CH chondrites are different from porphyritic chondrules in other carbonaceous chondrites ( [Krot et al., 2005], [Krot et al., 2008a] and [Krot et al., 2008b]). In order to test these hypotheses, we measured in situ oxygen isotopic compositions of porphyritic (magnesian, Type I and ferroan, Type II) and non-porphyritic (magnesian and ferroan cryptocrystalline) chondrules from Isheyevo and CB_b chondrites MAC 02675 and QUE 94627, paired with QUE 94611, using a Cameca ims-1280 ion microprobe.On a three-isotope oxygen diagram (δ¹⁷O vs. δ¹⁸O), compositions of chondrules measured follow approximately slope-1 line. Data for 19 magnesian cryptocrystalline chondrules from Isheyevo, 24 magnesian cryptocrystalline chondrules and 6 magnesian cryptocrystalline silicate inclusions inside chemically-zoned Fe,Ni-metal condensates from CB_b chondrites have nearly identical compositions: Δ¹⁷O = −2.2 ± 0.9‰, −2.3 ± 0.6‰ and −2.2 ± 1.0‰ (2σ), respectively. These observations and isotopically light magnesium compositions of cryptocrystalline magnesian chondrules in CB_b chondrites (Gounelle et al., 2007) are consistent with their single-stage origin, possibly as gas-melt condensates in an impact-generated plume. In contrast, Δ¹⁷O values for 11 Type I and 9 Type II chondrules from Isheyevo range from −5‰ to +4‰ and from −17‰ to +3‰, respectively. In contrast to typical chondrules from carbonaceous chondrites, seven out of 11 Type I chondrules from Isheyevo plot above the terrestrial fractionation line. We conclude that (i) porphyritic chondrules in Isheyevo belong to a unique population of objects, suggesting formation either in a different nebular region or at a different time than chondrules from other carbonaceous chondrites; (ii) Isheyevo, CB and CH chondrites are genetically related meteorites: they contain non-porphyritic chondrules produced during the same highly-energetic event, probably large-scale asteroidal collision; (iii) the differences in mineralogy, petrography, chemical and whole-rock oxygen isotopic compositions between CH and CB chondrites are due to various proportions of the nebular and the impact-produced materials.     

Solvation processes in steam: Ab initio calculations of ion-solvent structures and clustering equilibria

Reports of the high ion content of steam and low-density supercritical fluids date back to the work of Carlon [Carlon H. R. (1980) Ion content of air humidified by boiling water.J. Appl.Phys.51, 171-173], who invoked ion and neutral-water clustering as mechanism to explain why ions partition into the low-density aqueous phase. Mass spectrometric, vibrational spectroscopic measurements and quantum chemical calculations have refined this concept by proposing strongly bound ion-solvent aggregates and water clusters such as Eigen- and Zundel-type proton clusters H₃O⁺·(H₂O)_m and the more weakly bound water oligomers (H₂O)_m. The extent to which these clusters affect fluid chemistry is determined by their abundance, however, little is known regarding the stability of such moieties in natural low-density high-temperature fluids. Here we report results from quantum chemical calculations using chemical-accuracy multi-level G3 (Curtiss-Pople) and CBS-Q theory (Peterson) to address this question. In particular, we have investigated the cluster structures and clustering equilibria for the ions and H₃S⁺·(H₂O)_m(H₂S)_n, where m ? 6 and n ? 4, at 300-1000 K and 1 bar as well as under vapor-liquid equilibrium conditions between 300 and 646 K. We find that incremental hydration enthalpies and entropies derived from van’t Hoff analyses for the attachment of H₂O and H₂S onto H₃O⁺, and H₃S⁺ are in excellent agreement with experimental values and that the addition of water to all three ions is energetically more favorable than solvation by H₂S. As clusters grow in size, the energetic trends of cluster hydration begin to reflect those for bulk H₂O liquids, i.e. calculated hydration enthalpies and entropies approach values characteristic of the condensation of bulk water (ΔH^o = −44.0 kJ mol⁻¹, ΔS^o = −118.8 J K mol⁻¹). Water and hydrogen sulfide cluster calculations at higher temperatures indicate that a significant fraction of H₃O⁺, and H₃S⁺ ions exists as solvated moieties.     

Organic matter and metamorphic history of CO chondrites

The metamorphic grades of a series of eight CO3 chondrites (ALHA77307, Colony, Kainsaz, Felix, Lancé, Ornans, Warrenton and Isna) have been quantified. The method used was based on the structural grade of the organic matter trapped in the matrix, which is irreversibly transformed by thermal metamorphism. The maturation of the organic matter is independent with respect to the mineralogical context and aqueous alteration. This metamorphic tracer is thus valid whatever the chemical class of chondrites. Moreover, it is sensitive to the peak metamorphic temperature.The structural grade of the organic matter was used along with other metamorphic tracers such as petrography of opaque minerals, Fa and Fs silicate composition in type I chondrules, presolar grains and noble gas (P3 component) abundance. The deduced metamorphic hierarchy and the attributed petrographic types are the following: ALHA77307 (3.03) < Colony (3.1) < Kainsaz (3.6) < Felix (3.6 (1)) < Ornans (3.6 (2)) < Lancé (3.6 (3)) < Warrenton (3.7 (1)) < Isna (3.7 (2)).For most metamorphosed objects, the peak metamorphic temperature can be estimated using a geothermometer calibrated with terrestrial metasediments [Beyssac O., Goffe B., Chopin C., and Rouzaud J. N. (2002) Raman spectrum of carbonaceous material in metasediments: a new geothermometer. J. Metamorph. Geol., 20, 859-871]. A value of 330 °C was obtained for Allende (CV chondrite), Warrenton and Isna, consistent with temperatures estimated from Fe diffusion [Weinbruch S., Armstrong J., and Palme H. (1994). Constraints on the thermal history of the Allende parent body as derive from olivine-spinel thermometry and Fe/Mg interdiffusion in olivine. Geochim. Cosmochim. Acta58(2), 1019-1030.], from the Ni content in sulfide-metal assemblages [Zanda B., Bourot-Denise M., and Hewins R. (1995) Condensate sulfide and its metamorphic transformations in primitive chondrites. Meteorit. Planet. Sci.30, A605.] and from the d₀₀₂ interlayer spacing in poorly graphitized carbon [Rietmeijer, F., and MacKinnon, I. (1985) Poorly graphitized carbon as a new cosmothermometer for primitive extraterrestrial materials. Nature, 315, 733-736]. The trapped noble gas and C content appear to be sensitive but not precise metamorphic tracers, indicating that the “Ornans paradox” does not exist. Major problems with the current petrologic types derived from Induced ThermoLuminescence are pointed out.     

The thermal history of equilibrated ordinary chondrites and the relationship between textural maturity and temperature

The compositions and textures of phases in eleven equilibrated ordinary chondrites from the H, L, and LL groups spanning petrographic types 4-6 were studied and used to constrain the thermal histories of their parent bodies. Based on Fe-Mg exchange between olivine and spinel, average equilibration temperatures for type 4-6 chondrites encompass a small range, 586-777 °C, relative to what is commonly assumed for peak temperatures (600-950 °C). The maximum temperatures recorded by individual chondrites, which are minima relative to peak metamorphic temperatures, increase subtly but systematically with metamorphic type and are tightly clustered for H4-6 (733-754 °C) and LL4-6 (670-777 °C). For the Ls, Ausson (L5) records a higher maximum olivine-spinel temperature (761 °C) than does the L4 chondrite Saratov (673 °C) or the L6 chondrite Glatton (712 °C). Our data combined with olivine-spinel equilibration temperatures calculated for other equilibrated ordinary chondrites using mineral compositions from the literature demonstrate that, in general, type 4 chondrites within each chemical group record temperatures lower than or equal to those of types 5-6 chondrites.For H chondrites, the olivine-spinel closure temperature is a function of spinel grain size, such that larger grains, abundant in types 5-6 chondrites, record temperatures of ∼740 °C or more while smaller grains, rare in types 5-6 but abundant in type 4 chondrites, record lower temperatures. Olivine-spinel temperatures in the type 6 chondrites Guareña and Glatton are consistent with rapid (50-100 °C/Myr) cooling from high temperatures in the ordinary chondrite parent bodies. With one exception (∼500 °C/Myr), olivine-spinel data for St.-Séverin (LL6) are consistent with similar cooling rates. Cooling rates of order 100 °C/Myr at ∼750 °C for type 6 chondrites are considerably higher than previously determined cooling rates for lower temperatures (?550 °C) based on metallography, fission tracks, and geochronology. For H chondrites, current thermal models of an “onion shell” parent body are inconsistent with a small range of peak temperatures based on olivine-spinel and two pyroxene thermometry combined with a wide dispersion of cooling rates at low temperatures. Equilibrated chondrites may have sampled regions near a major transition in physical properties such as near the base of a regolith pile.     

Thermodynamic properties of anhydrous smectite MX-80, illite IMt-2 and mixed-layer illite-smectite ISCz-1 as determined by calorimetric methods. Part I: Heat capacities, heat contents and entropies

The heat capacities of the anhydrous international reference clay minerals, smectite MX-80, illite IMt-2 and mixed-layer illite-smectite ISCz-1, were measured by low temperature adiabatic calorimetry and differential scanning calorimetry, from 6 to 520 K (at 1 bar). The samples were chemically purified and Na-saturated. Dehydrated clay fractions <2 μm were studied. The structural formulae of the corresponding clay minerals, obtained after subtracting the remaining impurities, are K_0.026Na_0.435Ca_0.010(Si_3.612Al_0.388) (Al_1.593Mg_0.228Ti_0.011)O₁₀(OH)₂ for smectite MX-80, K_0.762Na_0.044(Si_3.387Al_0.613) (Al_1.427Mg_0.241O₁₀(OH)₂ for illite IMt-2 and K_0.530Na_0.135(Si_3.565Al_0.435)(Al_1.709Mg_0.218Ti_0.005)O₁₀(OH)₂for mixed-layer ISCz-1. From the heat capacity values, we determined the molar entropies, standard entropies of formation and heat contents of these minerals. The following values were obtained at 298.15 K and 1 bar:

	(J mol−1 K−1)	S0 (J mol−1 K−1)
Smectite MX-80	326.13 ± 0.10	280.56 ± 0.16
Illite IMt-2	328.21 ± 0.10	295.05 ± 0.17
Mixed-layer ISCz-1	320.79 ± 0.10	281.62 ± 0.15

Full-size table