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.     

Si‐bearing metal and niningerite in Almahata Sitta fine‐grained ureilites and insights into the diversity of metal on the ureilite parent body

A detailed mineralogical and chemical study of Almahata Sitta fine‐grained ureilites (MS‐20, MS‐165, MS‐168) was performed to shed light on the origin of these lithologies and their sulfide and metal. The Almahata Sitta fine‐grained ureilites (silicates <30 μm grain size) show textural and chemical evidence for severe impact smelting as described for other fine‐grained ureilites. Highly reduced areas in Almahata Sitta fine‐grained ureilites show large (up to ～1 mm) Si‐bearing metal grains (up to ～4.5 wt% Si) and niningerite [Mg_>0.5,(Mn,Fe)_<0.5S] with some similarities to the mineralogy of enstatite (E) chondrites. Overall, metal grains show a large compositional variability in Ni and Si concentrations. Niningerite grains probably formed as a by‐product of smelting via sulfidation. The large Si‐Ni variation in fine‐grained ureilite metal could be the result of variable degrees of reduction during impact smelting, inherited from coarse‐grained ureilite precursors, or a combination of both. Large Si‐bearing metal grains probably formed via coalescence of existing and newly formed metal during impact smelting. Bulk and in situ siderophile trace element abundances indicate three distinct populations of (1) metal crystallized from partial melts in MS‐20, (2) metal resembling bulk chondritic compositions in MS‐165, and (3) residual metal in MS‐168. Almahata Sitta fine‐grained ureilites developed their distinctive mineralogy due to severe reduction during smelting. Despite the presence of E chondrite and ureilite stones in the Almahata Sitta fall, a mixing relation of E chondrites or their constituents and ureilite material in Almahata Sitta can be ruled out based on isotopic, textural, and mineral‐chemical reasons.     

Ion Implants as Matrix‐Appropriate Calibrators for Geochemical Ion Probe Analyses

Ion microprobe elemental and isotopic determinations can be precise but difficult to quantify. Error is introduced when the reference material and the sample to be analysed have different compositions. Mitigation of such ‘matrix effects’ is possible using ion implants. If a compositionally homogeneous reference material is available which is ‘matrix‐appropriate’ (i.e., close in major element composition to the sample to be analysed, but having an unknown concentration of the element, E, to be determined) then ion implantation can be used to introduce a known amount of an E isotope, calibrating the E concentration and producing a matrix‐appropriate calibrator. Nominal implant fluences (ions cm^?2) are inaccurate by amounts up to approximately 30%. However, ion implantation gives uniform fluences over large areas; thus, it is possible to ‘co‐implant’ an additional reference material of any bulk composition having known amounts of E, independently calibrating the implant fluence. Isotope ratio measurement standards can be produced by implanting two different isotopes, but permil level precision requires postimplant calibration of the implant isotopic ratio. Examples discussed include (a) standardising Li in melilite; (b) calibrating a ²⁵Mg implant fluence using NIST SRM 617 glass and (c) using Si co‐implanted with ²⁵Mg alongside NIST SRM 617 to produce a calibrated measurement of Mg in Si.     

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.     

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.     

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.     

Petrogenesis of anomalous Queen Alexandra Range enstatite meteorites and their relation to enstatite chondrites,primitive enstatite achondrites,and aubrites

Queen Alexandra Range (QUE) meteorite 94204 is an anomalous enstatite meteorite whose petrogenesis has been ascribed to either partial melting or impact melting. We studied the meteorite pairs QUE 94204, 97289/97348, 99059/99122/99157/99158/99387, and Yamato (Y)‐793225; these were previously suggested to represent a new grouplet. We present new data for mineral abundances, mineral chemistries, and siderophile trace element compositions (of Fe,Ni metal) in these meteorites. We find that the texture and composition of Y‐793225 are related to EL6, and that this meteorite is unrelated to the QUEs. The mineralogy and siderophile element compositions of the QUEs are consistent with petrogenesis from an enstatite chondrite precursor. We caution that potential re‐equilibration during melting and recrystallization of enstatite chondrite melt‐rocks make it unreliable to use mineral chemistries to assign a specific parent body affinity (i.e., EH or EL). The QUEs have similar mineral chemistries among themselves, while slight variations in texture and modal abundances exist between them. They are dominated by inclusion‐bearing millimeter‐sized enstatite (average En_99.1–99.5) with interstitial spaces filled predominantly by oligoclase feldspar (sometimes zoned), kamacite (Si approximately 2.4 wt%), troilite (≤2.4 wt% Ti), and cristobalite. Siderophile elements that partition compatibly between solid metal and liquid metal are not enriched like in partial melt residues Itqiy and Northwest Africa (NWA) 2526. We find that the modal compositions of the QUEs are broadly unfractionated with respect to enstatite chondrites. We conclude that a petrogenesis by impact melting, not partial melting, is most consistent with our observations.     

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.