J. N. Grossman

Highly siderophile elements in chondrites

Abstract The abundances of the highly siderophile elements (HSE), Re, Os, Ir, Ru, Pt and Pd, were determined by isotope dilution mass spectrometry for bulk samples of 13 carbonaceous chondrites, 13 ordinary chondrites and 9 enstatite chondrites. These data are coupled with corresponding 187Re–187Os isotopic data reported by Walker et al. [Geochim. Cosmochim. Acta, 2002] in order to constrain the nature and timing of chemical fractionation relating to these elements in the early solar system. The suite of chondrites examined displays considerable variations in absolute abundances of the HSE, and in the ratios of certain HSE. Absolute abundances of the HSE vary by nearly a factor of 80 among the chondrite groups, although most vary within a factor of only 2. Variations in concentration largely reflect heterogeneities in the sample aliquants. Different aliquants of the same chondrite may contain variable proportions of metal and/or refractory inclusions that are HSE-rich, and sulfides that are HSE-poor. The relatively low concentrations of the HSE in CI1 chondrites likely reflect dilution by the presence of volatile components. Carbonaceous chondrites have Re/Os ratios that are, on average, approximately 8% lower than ratios for ordinary and enstatite chondrites. This is also reflected in 187Os/188Os ratios that are approximately 3% lower for carbonaceous chondrites than for ordinary and enstatite chondrites. Given the similarly refractory natures of Re and Os, this fractionation may have occurred within a narrow range of high temperatures, during condensation of these elements from the solar nebula. Superimposed on this major fractionation are more modest movements of Re or Os that occurred within the last 0–2 Ga, as indicated by minor open-system behavior of the Re–Os isotope systematics of some chondrites. The relative abundances of other HSE can also be used to discriminate among the major classes of chondrites. For example, in comparison to the enstatite chondrites, carbonaceous and ordinary chondrites have distinctly lower ratios of Pd to the more refractory HSE (Re, Os, Ir, Ru and Pt). Differences are particularly well resolved for the EH chondrites that have Pd/Ir ratios that average more than 40% higher than for carbonaceous and ordinary chondrite classes. This fractionation probably occurred at lower temperatures, and may be associated with fractionation processes that also affected the major refractory lithophile elements. Combined, 187Os/188Os ratios and HSE ratios reflect unique early solar system processing of HSE for each major chondrite class.

Comparative 187Re-187Os systematics of chondrites: Implications regarding early solar system processes

Abstract A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the 187Re/188Os and 187Os/188Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average 187Re/188Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the 187Os/188Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history. A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga. The 187Os/188Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.

Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California

The abundance, P-T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600°C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high-T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of “average” island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H2O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. “Exotic” LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by “subduction-zone metasomatism,” although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments.

Rhenium-Osmium Isotope Constraints on the Age of Iron Meteorites

Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately �31 million years for meteorites ∼4500 million years old. Although an absolute rheniumosmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of 187Re, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isocbron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

Rhenium-osmium isotope systematics in meteorites. I - Magmatic iron meteorite groups IIAB and IIIAB

Abstract Using resonance ionization mass spectrometry (RIMS), Re and Os abundances were determined by isotope dilution (ID) and 187 Os/ 186 Os ratios measured in nineteen iron meteorites: eight from group IIAB, ten from group IIIAB, and Treysa (IIIB anomalous). Abundances range from 1.4 to 4800 ppb Re, and from 13 to 65000 ppb Os, and generally agree well with previous ID and neutron activation (NAA) results. The Re and Os data suggest that abundance trends in these iron groups may be entirely explained by fractional crystallization. Addition of late-formed metal to produce Re Os variation in the B subgroups is not essential but cannot be excluded. Whole-rock isochrons for the IIAB and IIIAB groups are statistically indistinguishable. Pooled data yield an initial 187 Os/ 186 Os of 0.794 ± 0.010, with a slope of (7.92 ± 0.20) × 10 −2 corresponding to a magmatic iron meteorite age of 4.65 ± 0.11 Ga (using a decay constant of 1.64 × 10 −11 a −1 ). Given the errors in the slope and half life, this age does not differ significantly from the canonical chondrite age of 4.56 Ga, but could be as young as 4.46 Ga.