The oxidation state of an olivine phenocryst separate from clinopyroxene-olivine andesitic black scoria with red-brown tint from Kasayama volcano, Hagi, Yamaguchi Prefecture, was determined using 57Fe Mössbauer spectroscopy, to examine the effect of high temperature oxidation on the oxidation state of Fe. The olivine phenocrysts examined were euhedral to subhedral in form, typically fractured, and about 0.2-1 mm in maximum dimension. Small amounts of Fe-bearing precipitate minerals often occur on the rims of olivine phenocrysts in the black scoria with red-brown tint, and near subhedral Cr-rich magnetite with about 5 μm in diameter. Olivine phenocrysts lacking such precipitates and inclusions were separated from a sample using an isodynamic separator and handpicking under a binocular microscope. Examination by optical microscopy, electron microprobe analysis, Raman spectroscopy, and high-resolution transmission microscopy proved no precipitates in the separated olivine phenocrysts. Average Fo value and Fe content of the olivines were 81 mol% and 0.36 atoms per formula unit (apfu), respectively. The 57Fe Mössbauer spectrum of the olivine separate consisted of three doublets assigned to Fe2+ at the M1, Fe2+ at the M2 and Fe3+ at the octahedral sites. The Fe2+:Fe3+-ratio is 95(3):5(1). By applying this value to the average Fe content, Fe2+ and Fe3+ are calculated to be 0.34(1) and 0.018(4) apfu, respectively. Since the Fe3+ within olivine detected in this study is not due to any Fe3+-bearing impurity, Fe3+ could be located at the octahedral site within the olivine structure. The quadrupole splitting value of the Fe3+-Mössbauer doublet [0.53(5) mm/s] in Kasayama olivine is significantly lower than published data for Fe3+ at the M2 site in olivine, and in laihunite. This suggests possible distribution of Fe3+ at the M1 site. Fe3+ within olivine in the black scoria with red-brown tint is considered to have been generated at high temperatures (perhaps above 800 °C).
The structure of quatrandorite is reported for the first time from an untwinned sample from Oura mine, San Jose, Bolivia. The mineral crystallizes in P21/c, a = 19.1686 (19) Å, b = 17.160 (3) Å, c = 13.042 (2) Å, β = 90.008 (12)°, V = 4289.9 (11) Å3, Z = 4. Refinement to Robs = 5.66% was obtained with Jana2006. Quatrandorite belongs to the andorite series, whose members share two cell parameters while the third can be expressed as n × 4.3 Å, with n = 2, 4 and 6 for ramdohrite (uchucchacuaite, fizelyite), quatrandorite and senandorite, respectively. Both quatrandorite and senandorite are strongly pseudosymmetric up to Cmcm with one parameter corresponding to n = 1 (∼ 4.3 Å). The hypothetical structure corresponding to Cmcm is also the aristotype common to both minerals. The strong structural similarity of quatrandorite and senandorite may explain their co-existence in some samples, which has in the past led to hypothesize the existence of a further member of the series, nakaséite, which was however later shown to consist of a random stacking of the two minerals. The Cmcm aristotype is not common to the n = 2 minerals (uchucchacuaite, ramdohrite, fizelyite), which are thus structurally less closely related to the two other members. A common aristotype to all three minerals can nevertheless be obtained via a different path, which leads to Cmme with the same cell parameters as Cmcm; the degree of pseudo-symmetry in this supergroup is however lower and there remain a difference in one sulfur position in this aristotype. It nevertheless confirms previous reports in the literature stating that the bulk of the structure of the minerals of this series can be reduced to a common principle, essentially a distorted galena; the departures from it are however crucial for the realization of the individual structures.
Adsorption experiments of Zn onto ferrihydrite were carried out at different initial Fe concentrations and pH, and at room temperature. Zinc-adsorbed ferrihydrite was fractionated to examine Zn adsorption among different-size aggregates of ferrihydrite. Primary ferrihydrite particles were as small as 5-7 nm in diameter and they formed aggregates of <0.25 to >32 μm in size. The dominant size of the aggregates decreased with a decrease in the initial Fe concentrations and pH. Zinc was adsorbed on the surface of individual ferrihydrite nano-particles but not on that of ferrihydrite aggregates, indicating that ferrihydrite nano-particles were so loosely attached to one another in aggregates that individual nano-particles could adsorb Zn. The size distribution of ferrihydrite aggregates and the Zn adsorption on individual ferrihydrite nano-particles can change the sedimentation rate of ferrihydrite aggregates and the behavior of Zn during the transformation of ferrihydrite to goethite and hematite. Therefore, our results will give a deeper understanding of metal transport by ferrihydrite.
Os isotopic composition (187Os/188Os = 0.1235) of a refractory harzburgite in the Hayachine-Miyamori ophiolite is subchondritic, indicating the long-term depletion of Re. Such an unradiogenic Os isotopic signature is consistent with the less oxidized condition at subduction initiation. The major and trace element characteristics of the harzburgite, together with its petrography and relatively high modal abundance of clinopyroxene, suggest an involvement of a carbonate-rich silicate melt during melt extraction in arc setting.