Tungsten and hafnium distribution in calcium-aluminum inclusions (CAIs) from Allende and Efremovka

Recent ¹⁸²Hf-¹⁸²W age determinations on Allende Ca-, Al-rich refractory inclusions (CAIs) and on iron meteorites indicate that CAIs have initial ε¹⁸²W (−3.47 ± 0.20, 2σ) identical to that of magmatic iron meteorites after correction of cosmogenic ¹⁸²W burn-out (−3.47 ± 0.35, 2σ). Either the Allende CAIs were isotopically disturbed or the differentiation of magmatic irons (groups IIAB, IID, IIIAB, and IVB) all occurred <1 m.y. after CAI formation. To assess the extent of isotopic disturbance, we have analyzed the elemental distribution of Hf and W in two CAIs, Ef2 from Efremovka (CV3 reduced), and Golfball from Allende (CV3 oxidized). Fassaite is the sole host of Hf (10-25 ppm) and, therefore, of radiogenic W in CAIs, with ¹⁸⁰Hf/¹⁸⁴W > 10³, which is lowered by the ubiquitous presence of metal inclusions to ¹⁸⁰Hf/¹⁸⁴W > 10 in bulk fassaite. Metal alloy (Ni ∼ 50%) is the sole host of W (∼500 ppm) in Ef2, while opaque assemblages (OAs) and secondary veins are the hosts of W in Golfball. A large metal alloy grain from Ef2, EM2, has ¹⁸⁰Hf/¹⁸⁴W < 0.006. Melilite has both Hf and W below detection limits (<0.01 ppm), but the presence of numerous metallic inclusions or OAs makes melilite a carrier for W, with ¹⁸⁰Hf/¹⁸⁴W < 1 in bulk melilite. Secondary processes had little impact on the ¹⁸²Hf-¹⁸²W systematics of Ef2, but a vein cross-cutting fassaite in Golfball has >100 ppm W with no detectable Pt or S. This vein provides evidence for transport of oxidized W in the CAI. Because of the ubiquitous distribution of OAs, interpretations of the ¹⁸²Hf-¹⁸²W isochron reported for Allende CAIs include: (i) all W in the OAs was derived by alteration of CAI metal, or (ii) at least some of the W in OAs may have been equilibrated with radiogenic W during metamorphism of Allende. Since (ii) cannot be ruled out, new ¹⁸²Hf-¹⁸²W determinations on CAIs from reduced CV3 chondrites are needed to firmly establish the initial W isotopic composition of the solar system.     

Re-Os isotopic systematics and platinum group element composition of the Tagish Lake carbonaceous chondrite

The Tagish Lake meteorite is a primitive C2 chondrite that has undergone aqueous alteration shortly after formation of its parent body. Previous work indicates that if this type of material was part of a late veneer during terrestrial planetary accretion, it could provide a link between atmophile elements such as H, C, N and noble gases, and highly siderophile element replenishment in the bulk silicate portions of terrestrial planets following core formation. The systematic Re-Os isotope and highly siderophile element measurements performed here on five separate fractions indicate that while Tagish Lake has amongst the highest Ru/Ir (1.63 ± 0.08), Pd/Ir (1.19 ± 0.06) and ¹⁸⁷Os/¹⁸⁸Os (0.12564-0.12802) of all carbonaceous chondrites, these characteristics still fall short of those necessary to explain the observed siderophile element systematics of the primitive upper mantles of Earth and Mars. Hence, a direct link between atmophile and highly siderophile elements remains elusive, and other sources for replenishment are required, unless an as yet poorly constrained process fractionated Re/Os, Ru/Ir, and Pd/Ir following late accretion on both the Earth and Mars mantles.The unique elevated Ru/Ir combined with elevated ¹⁸⁷Os/¹⁸⁸Os of Tagish Lake may be attributed to Ru and Re mobility during aqueous alteration very early in its parent body history. The Os, Ir, Pt, and Pd abundances of Tagish Lake are similar to CI chondrites. The elevated Ru/Ir and the higher Re/Os and consequent ¹⁸⁷Os/¹⁸⁸Os in Tagish Lake, are balanced by a lower Ru/Ir and lower Re/Os and ¹⁸⁷Os/¹⁸⁸Os in CM-chondrites, relative to CI chondrites. A model that links Tagish Lake with CI and CM chondrites in the same parent body may explain the observed systematics. In this scenario, CM chondrite material comprises the exterior, grading downward to Tagish Lake material, which grades to CI material in the interior of the parent body. Aqueous alteration intensifies towards the interior with increasing temperature. Ruthenium and Re are mobilized from the CM layer into the Tagish Lake layer. This model may thus provide a potential direct parent body relationship between three separate groups of carbonaceous chondrites.     

Highly siderophile elements in ureilites

The abundances of the highly siderophile elements (HSE) Ru, Pd, Re, Os, Ir, and Pt were determined by isotope dilution mass spectrometry for 22 ureilite bulk rock samples, including monomict, augite-bearing, and polymict lithologies. This report adds significantly to the quantity of available Pt and Pd abundances in ureilites, as these elements were rarely determined in previous neutron activation studies. The CI-normalized HSE abundance patterns of all ureilites analyzed here except ALHA 81101 show marked depletions in the more volatile Pd, with CI chondrite-normalized Pd/Os ratios (excluding ALHA 81101) averaging 0.19 ± 0.23 (2σ). This value is too low to be directly derived from any known chondrite group. Instead, the HSE bulk rock abundances and HSE interelement ratios in ureilites can be understood as physical mixtures of two end member compositions. One component, best represented by sample ALHA 78019, is characterized by superchondritic abundances of refractory HSE (RHSE—Ru, Re, Os, Ir, and Pt), but subchondritic Pd/RHSE, and is consistent with residual metal after extraction of a S-bearing metallic partial melt from carbonaceous chondrite-like precursor materials. The other component, best represented by sample ALHA 81101, is RHSE-poor and has HSE abundances in chondritic proportions. The genesis of the second component is unclear. It could represent regions within the ureilite parent body (UPB), in which metallic phases were completely molten and partially drained, or it might represent chondritic contamination that was added during disruption and brecciation of the UPB. Removal of carbon-rich melts does not seem to play an important role in ureilite petrogenesis. Removal of such melts would quickly deplete the ureilite precursors in Re/Os and As/Au, which is inconsistent with measured osmium isotope abundances, and also with literature As/Au data for the ureilites. Removal of ²⁶Al during silicate melting may have acted as a switch that turned off further metal extraction from ureilite source regions.     

Formation of metal in the CH chondrites ALH 85085 and PCA 91467

Siderophile element distributions within individual metal grains in two CH chondrites, Allan Hills 85085 and Pecora Escarpment 91467, were measured by laser ablation inductively coupled plasma mass spectrometry. Those metal grains that are zoned in Ni were also found to be zoned in other refractory siderophile elements, such as Ru, but not in Pd, which is not refractory but is highly siderophile. This pattern is consistent with an origin by condensation from a gas of approximately solar composition, but not with an origin by redox processes or fractional crystallization. The unzoned metal grains in CH chondrites were found to be frequently depleted in Ru but not in Pd, consistent with later stage condensation from a solar gas after removal of the zoned metal. Gold is inversely correlated with Ni in the unzoned metal grains, and mean Au abundances in zoned metal are always low. Both zoned and unzoned metal in CH chondrites could plausibly be produced from a thermostatically regulated nebula, followed by rapid removal of the zoned metal, and slower removal of the unzoned metal, both at temperatures near or above the condensation temperature of Au (∼1250 K). This is also consistent with the isolation temperatures inferred from silicate grains in CH chondrites by previous workers based on their volatile element inventories. The volatile siderophile Cu is enriched in the rims relative to the interiors of both zoned and unzoned grains, and is interpreted as the product of diffusion during low-grade thermal processing. The similarity of Cu distributions, and degree of kamacite/taenite exsolution, between zoned and unzoned metal in CH chondrites suggests that the two populations of metal experienced modest thermal metamorphism after they were brought together in the same environment, probably on the CH parent body. Fragmentation and size-sorting of the metal must have post-dated the Cu zoning, and may have occurred in a regolith on the CH parent body. The compositions of CH metal, like that of metal from QUE 94411 and HH 237, are consistent with a nebular origin, and may be the most primitive nebular materials (as distinct from presolar grains) sampled by chondrites.     

Natural variations in the rhenium isotopic composition of meteorites

Rhenium is an important element with which to test hypotheses of isotope variation. Historically, it has been difficult to precisely correct the instrumental mass bias in thermal ionization mass spectrometry. We used W as an internal standard to correct mass bias on the MC‐ICP‐MS, and obtained the first precise δ¹⁸⁷Re values (~±0.02‰, 2SE) for iron meteorites and chondritic metal. Relative to metal from H chondrites, IVB irons are systematically higher in δ¹⁸⁷Re by ~0.14 ‰. δ¹⁸⁷Re for other irons are similar to H chondritic metal, although some individual samples show significant isotope fractionation. Since ¹⁸⁵Re has a high neutron capture cross section, the effect of galactic cosmic‐ray (GCR) irradiation on δ¹⁸⁷Re was examined using correlations with Pt isotopes. The pre‐GCR irradiation δ¹⁸⁷Re for IVB irons is lower, but the difference in δ¹⁸⁷Re between IVB irons and other meteoritic metal remains. Nuclear volume‐dependent fractionation for Re is about the right magnitude near the melting point of iron, but because of the refractory and compatible character of Re, a compelling explanation in terms of mass‐dependent fractionation is elusive. The magnitude of a nucleosynthetic s‐process deficit for Re estimated from Mo and Ru isotopes is essentially unresolvable. Since thermal processing reduced nucleosynthetic effects in Pd, it is conceivable that Re isotopic variations larger than those in Mo and Ru may be present in IVBs since Re is more refractory than Mo and Ru. Thus, the Re isotopic difference between IVBs and other irons or chondritic metal remains unexplained.     

Stepwise,earthquake-driven coastal subsidence in the Ganges–Brahmaputra Delta (Sundarbans) since the eighth century deduced from submerged in situ kiln and mangrove remnants

Natural Hazards - This study reconstructs the coastal subsidence over the past 1300&nbsp;years in a mangrove region along the coast of the Ganges–Brahmaputra Delta, an area not affected...     

Nickeliferous pyrite tracks pervasive hydrothermal alteration in Martian regolith breccia: A study in NWA 7533

Martian regolith breccia NWA 7533 (and the seven paired samples) is unique among Martian meteorites in showing accessory pyrite (up to 1% by weight). Pyrite is a late mineral, crystallized after the final assembly of the breccia. It is present in all of the lithologies, i.e., the fine‐grained matrix (ICM), clast‐laden impact melt rocks (CLIMR), melt spherules, microbasalts, lithic clasts, and mineral clasts, all lacking magmatic sulfides due to degassing. Pyrite crystals show combinations of cubes, truncated cubes, and octahedra. Polycrystalline clusters can reach 200 μm in maximum dimensions. Regardless of their shape, pyrite crystals display evidence of very weak shock metamorphism such as planar features, fracture networks, and disruption into subgrains. The late fracture systems acted as preferential pathways for partial replacement of pyrite by iron oxyhydroxides interpreted as resulting from hot desert terrestrial alteration. The distribution and shape of pyrite crystals argue for growth at moderate to low growth rate from just‐saturated near neutral (6 < pH<10), H₂S‐HS‐rich fluids at minimum log fO₂ of >FMQ + 2 log units. It is inferred from the maximum Ni contents (4.5 wt%) that pyrite started crystallizing at 400–500 °C, during or shortly after a short‐duration, relatively low temperature, thermal event that lithified and sintered the regolith breccias, 1.4 Ga ago as deduced from disturbance in several isotope systematics.     

Chondrule cooling rates inferred from diffusive profiles in metal lumps from the Acfer 097 CR2 chondrite

Abstract— CR chondrites contain metal lumps (>300 μm) either attached to chondrule silicates or apparently isolated in the matrix. Here, laser ablation microanalysis of six metal lumps from a polished thin section of the Acfer 097 CR2 chondrite at 15 μm spatial resolution revealed zoning profiles for the volatile elements Cu and Ga. The mutual diffusivities of Cu and Ga were used to infer T ～ 1473 ± 100 K from the correlation of Cu versus Ga. The cooling rates of the metal lumps were calculated to be 0.5–50 K h^?1 for T_p ～ 1473 ± 100 K, with a maximum possible range of 0.1–400 K h^?1 for T_p ～ 1200–1800 K, overlapping the range of cooling rates inferred from petrological studies of type I chondrules (10–1000 K h^?1). Chondrule textures were established near the peak heating temperatures of chondrules (approximately 1900–2000 K), while the Cu and Ga diffusive profiles were established after solidification (T ～ 1500 K), consistent with nonlinear cooling. Furthermore, one chondrule (N2) has a more complex zoning profile that is modeled as a three‐stage cooling history involving initial cooling at approximately 1 K h^?1, followed by mild re‐heating (T ～ 1700 K) that re‐evaporated Cu and Ga from the outer approximately 100 μm of the metal lump and then cooled again at approximately 5 K h^?1. The thermal effects of parent body and other preaccretionary heating events on the Cu and Ga zoning profiles are examined. Although CR parent bodies have experienced aqueous alteration, the thermal effects of this process can neither produce nor erase the Cu and Ga diffusive profiles. Thus, metal lumps in CR chondrites record the solid‐state thermal history of chondrules as they travelled away from the chondrule‐forming region.     

Iron/manganese ratio and manganese content in shield lavas from Ko’olau Volcano, Hawai’i

Precise Fe/Mn ratios and MnO contents have been determined for basalts from the Hawaiian shields of Ko’olau and Kilauea by inductively coupled plasma mass spectrometry. It is well known that the youngest Ko’olau (Makapu’u-stage) shield lavas define a geochemical endmember for Hawaiian lavas in terms of CaO and SiO₂ contents and isotopic ratios of O, Sr, Nd, Hf, Pb, and Os. We find that their MnO content is also distinct. Despite the small range in MnO, 0.146 to 0.176 wt%, the precision of our data is sufficient to show that among unaltered Ko’olau lavas MnO content is correlated with Nd-Hf-Pb isotopic ratios, La/Nb and Al₂O₃/CaO elemental ratios, and contents of SiO₂, MgO and Na₂O + K₂O adjusted for olivine fractionation. These trends are consistent with two-component mixing; one endmember is a SiO₂-rich, MnO-, and MgO-poor dacite or andesite melt, generated by low degree (10-20%) partial melting of eclogite. Since this low-MgO endmember (dacite or andesite melt) has very low FeO and MnO contents, mixing of high Fe/Mn dacite or andesite melt with a MgO-rich picritic melt, the other endmember, does not significantly increase the Fe/Mn in mixed magmas; consequently, Ko’olau and Kilauea lavas have similar Fe/Mn. We conclude that the high Fe/Mn in Hawaiian lavas relative to mid-ocean ridge basalt originates from the high MgO endmember in Hawaiian lavas.     

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.