Search

We have determined the valence state of Ytterbium (Yb) in a collection of meteorites covering 4–5 orders of magnitude in oxygen fugacity (fO 2) by X-ray absorption near-edge structure (XANES) spectroscopy at the Yb L2 edge. In the studied meteorite minerals, Yb abundance was between 1 and 30 ppm. The data were obtained from merrillite grains (theoretical formula Ca 18 Na 2 Mg 2 (PO 4) 14) from two equilibrated ordinary chondrites (one H6 and one LL6), on oldhamite grains (theoretical formula CaS) from three EH enstatite chondrites (from EH3 to EH5) and four EL enstatite chondrites (from EL3 to EL6), on one merrilite grain and one stanfieldite grain (theoretical formula Ca 4 (Mg,Fe,Mn) 5 (PO 4) 6) from a pallasite, on merrillite grains from a eucrite, and in a phosphorous-bearing phase from an ungrouped primitive achondrite (NWA 11119). The obtained Yb XANES spectra were compared to those measured in terrestrial apatites (containing 17–79 ppm Yb) and in synthetic materials (metallic Yb, YbS, Yb 2 S 3 , Yb 2 O 3). In terrestrial apatites, as well as in ordinary chondrites, in the eucrite, in the pallasite, and in the ungrouped achondrite NWA 11119, Yb is present as Yb3+ only. In enstatite chondrites, about half of the Yb in CaS is in the Yb2+ form and the fraction of Yb2+ may be slightly higher in EH compared to EL. It appears that Yb redox state can be used to build a redox scale for the most reduced objects of the Solar System as shown by this slight difference between EH and EL. However, the absence of a strong difference in Yb redox state between EH and EL chondrites suggests that the observed difference in Yb abundance anomalies in oldhamites found between EH and EL is not due to oxygen fugacity prevailing during parent-body equilibration but rather to fractionation related to volatility. [ABSTRACT FROM AUTHOR]

In order to investigate the influence of very reducing conditions, we report enstatite-melt trace element partition coefficients (D) obtained on enstatite chondrite material at 5GPa and under oxygen fugacities (fO2) ranging between 0.8 and 8.2log units below the iron–wustite (IW) buffer. Experiments were conducted in a multianvil apparatus between 1580 and 1850°C, using doped (Sc, V, REE, HFSE, U, Th) starting materials. We used a two-site lattice strain model and a Monte-Carlo-type approach to model experimentally determined partition coefficient data. The model can fit our partitioning data, i.e. trace elements repartition in enstatite, which provides evidence for the attainment of equilibrium in our experiments. The precision on the lattice strain model parameters obtained from modelling does not enable determination of the influence of intensive parameters on crystal chemical partitioning, within our range of conditions (fO2, P, T, composition). We document the effect of variable oxygen fugacity on the partitioning of multivalent elements. Cr and V, which are trivalent in the pyroxene at around IW−1 are reduced to 2+ state with increasingly reducing conditions, thus affecting their partition coefficients. In our range of redox conditions Ti is always present as a mixture between 4+ and 3+ states. However the Ti3+-Ti4+ ratio increases strongly with increasingly reducing conditions. Moreover in highly reducing conditions, Nb and Ta, that usually are pentavalent in magmatic systems, appear to be reduced to lower valence species, which may be Nb2+ and Ta3+. We propose a new proxy for fO2 based on D(Cr)/D(V). Our new data extend the redox range covered by previous studies and allows this proxy to be used in the whole range of redox conditions of the solar system objects. We selected trace-element literature data of six chondrules on the criterion of their equilibrium. Applying the proxy to opx-matrix systems, we estimated that three type I chondrules have equilibrated at IW−7±1, one type I chondrule at IW−4±1, and two type II chondrules at IW+3±1. This first accurate estimation of enstatite-melt fO2 for type I chondrules is very close to CAI values. [ABSTRACT FROM AUTHOR]

Abstract: We present new Sr–Nd isotope compositions together with major- and trace element concentrations measured for whole rocks and mineral separate phases (apatite, biotite and calcite) from fifteen Cape Verde oceanic carbonatites (Atlantic Ocean). Trace element patterns of calcio- and magnesio-carbonatites present a strong depletion in K, Hf, Zr and Ti and an overall enrichment in Sr and REE relative to Cape Verde basalts, arguing for distinct source components between carbonatites and basalts. Sr and Nd isotopic ratios show small, but significant variations defining a binary mixing between a depleted end-member with unradiogenic Sr and radiogenic Nd values and a ‘‘enriched’’ end-member compatible with old marine carbonates. We interpret the depleted end-member as the Cape Verde oceanic lithosphere by comparison with previous studies on Cape Verde basalts. We thus propose that oceanic carbonatites are resulting from the interaction of a deep rooted mantle plume carrying a lower 4He/3He signature from the lower mantle and a carbonated metasomatized lithosphere, which by low degree melting produced carbonatite magmas. Sr–Nd compositions and trace element patterns of carbonatites argue in favor of a metasomatic agent originating from partial melting of recycled, carbonated oceanic crust. We have successfully reproduced the main geochemical features of this model using a Monte-Carlo-type simulation. [ABSTRACT FROM AUTHOR]

Abstract: We have measured apatite solubility in calcic carbonatitic liquids and determined apatite/melt partition coefficients for a series of trace elements, including the rare earth elements (REE), high field strength elements (HFSE), Rb, Sr, U–Th–Pb. Experiments were performed between 4 and 6GPa, from 1200 to 1380°C, using the multianvil apparatus. Trace element concentrations were determined by laser ablation ICP-MS and electron microprobe. In addition, a specific protocol was designed to measure carbon concentration in the apatites, using the electron microprobe. Two starting apatite samples were used in order to test for the effect of apatite chemistry on partitioning behavior. Apatite solubility is lower in calcitic melts by a factor 3–5 compared to dolomitic melts (3–5.5 vs. 10–18wt.% P2O5 in melt). We interpret this difference in terms of solubility product in the liquid and propose an empirical model for apatite saturation that takes into account melt calcium content. We conclude that calcitic melts that may form by melting of carbonated eclogites could be saturated with residual apatite, contrary to dolomitic melts formed in carbonated peridotites. Compatibility behavior of the REE depends on apatite silica content: REE are compatible in apatites containing 3.5–5wt.% SiO2, with values between 1.5 and 4, whereas REE are incompatible in apatites containing 0.2wt.% SiO2. HFSE, U, Th, and Y are compatible in silica-rich apatite, with while . Strontium is always retained in the melt, with of the order of 0.5. Lead appears to be incompatible in apatite, although this finding is weakened by almost complete Pb loss to sample container. High silica concentration favors REE incorporation in apatite by allowing for charged balanced coupled substitution. Sulfur and carbonate may also favor REE incorporation in apatite. Our results allow to reconcile previously published experimental determinations of REE partitioning. We use our experimentally determined partition coefficients to investigate the impact of residual apatite during partial melting of recycled carbonated material (eclogite+sediments) and discuss how the chemical characteristics of the produced liquids can be affected by residual apatite. [Copyright &y& Elsevier]

Abstract: The occurrence of CO2-rich lavas (carbonatites, kimberlites) and carbonate-rich xenoliths provide evidence for the existence of carbonatitic melts in the mantle. To model the chemical composition of such melts in the deep mantle, we experimentally determined partition coefficients for 23 trace elements (including REE, U-Th, HFSE, LILE) between deep mantle minerals and carbonatite liquids at 20 and 25GPa and 1600°C. Under these conditions, majoritic garnet and CaSiO3 perovskite are the main reservoirs for trace elements. This study used both femtosecond LA-ICP-MS and SIMS techniques to measure reliable trace element concentrations. Comparison of the two techniques shows a general agreement, except for Sc and Ba. Our experimentally determined partition coefficients are consistent with the lattice strain model. The data suggest an effect of melt structure on partition coefficients in this pressure range. For instance, strain-free partition coefficient (D 0) for majorite–carbonatite melts do not follow the order of cation valence, , observed for majorite–CO2-free silicate melts. The newly determined partition coefficients were combined with trace element composition of majoritic garnets found as inclusions in diamond to model trace element patterns of deep-seated carbonatites. The result compares favorably with natural carbonatites. This suggests that carbonatites can originate from the mantle transition zone. [Copyright &y& Elsevier]

Window glass experiences permanent densification under high hydrostatic pressure, like amorphous silica but to a lesser extent. Comparable hydrostatic stresses are reached beneath a sharp indenter during indentation loading. The behavior of glass under very high pressure is therefore a key factor in understanding indentation deformation. A careful modelling of a Vickers indentation process, accounting for a newly determined pressure-densification constitutive law, allows for a quantitative estimation of the contribution of densification to the indentation strain. [Copyright &y& Elsevier]

High-pressure high-temperature experiments have been carried out up to 25 GPa and 2200°C in a multianvil press on assemblages made of silicates and iron-silicon alloys. At 20 GPa, silicon is extracted from the metal phase, forming stishovite reaction rims around metal grains. The silicon content in metal has been measured by analytical electron microscopy and electron microprobe. In contrast with earlier experiments, the present data were obtained by using silicon-rich metal alloys as starting materials instead of studying incorporation of silicon in initially silicon-free metal. As in most of previous studies carried out below 25 GPa, the silicon content in liquid metal increases with increasing pressure and with decreasing oxygen fugacity. The oxygen fugacity in most experiments was calculated by using two independent buffers: iron/ẅstite (IW) and SiO2/Si, allowing to link consistently the Fe contents in silicates, the Si contents in metal and the temperatures of the experiments. At oxygen fugacities 4 log units below IW, silicates are in equilibrium with Si-rich metallic alloys (up to 17 wt% of Si in metal at 20 GPa and 2200°C). Extrapolation to 2 log units below IW leads to less than 0.1 wt% Si in the metal phase. Presence of several wt% of silicon in the Earth’s core thus requires highly reduced initial materials that, if equilibrated at conditions relevant to small planets, should already contain significant amount of silicon dissolved in metal. [Copyright &y& Elsevier]