“Cr-Zr-Ca armalcolite” is a mineral originally found in Apollo samples five decades ago. However, no structural information has been obtained for this mineral. In this study, we report a new occurrence of “Cr-Zr-Ca armalcolite” and its associated mineral assemblage in an Mg-suite lithic clast (Clast-20) from the brecciated lunar meteorite Northwest Africa 8182. In this lithic clast, plagioclase (An = 88–91), pyroxene (Mg#[Mg/(Mg+Fe)] = 0.87–0.91) and olivine (Mg# = 0.86–0.87) are the major rock-forming minerals. Armalcolite and “Cr-Zr-Ca armalcolite” are observed with other minor phases including ilmenite, chromite, rutile, fluorapatite, merrillite, monazite, FeNi metal, and Fe-sulfide. Based on 38 oxygen atoms, the chemical formula of “Cr-Zr-Ca armalcolite” is (Ca0.99Na0.01)Σ1.00(Ti14.22Fe2.06Cr2.01 Mg1.20Zr0.54Al0.49Ca0.21Y0.05Mn0.04Ce0.03Si0.03La0.01Nd0.01Dy0.01)Σ20.91O38. Electron backscatter diffraction (EBSD) results reveal that the “Cr-Zr-Ca armalcolite” has a loveringite R3 structure, differing from the armalcolite Bbmm structure. The estimated hexagonal cell parameters a and c of “Cr-Zr-Ca armalcolite” are 10.55 and 20.85 Å, respectively. These structural and compositional features indicate that “Cr-Zr-Ca armalcolite” is loveringite, not belonging to the armalcolite family. Comparison with “Cr-Zr-Ca armalcolite” and loveringite of other occurrences implies that loveringite might be an important carrier of rare earth elements in lunar Mg-suite rocks. The compositional features of plagioclase and mafic silicate minerals in Clast-20 differ from those in other Mg-suite lithic clasts from Apollo samples and lunar meteorites, indicating that Clast-20 represents a new example of diverse lunar Mg-suite lithic clasts.
Thallium-bearing samples of alum-(K) and voltaite from the Fornovolasco mining complex (Apuan Alps, Tuscany, Italy) have been characterized through X‑ray diffraction, chemical analyses, micro-Raman, infrared (FTIR), Mössbauer, and X‑ray absorption spectroscopy (XAS). Alum-(K) occurs as anhedral colorless grains or rarely as octahedral crystals, up to 5 mm. Electron-microprobe analysis points to the chemical formula (K0.74Tl0.10)Σ0.84(Al0.84Fe0.14)Σ0.98S2.03O8·12H2O. The occurrence of minor was detected through FTIR spectroscopy. Its unit-cell parameter is a = 12.2030(2) Å, V = 1817.19(9) Å3, space group Its crystal structure has been refined down to R1 = 0.0351 for 648 reflections with Fo > 4σ(Fo) and 61 refined parameters. The crystal structure refinement agrees with the partial substitution of K by 12 mol% Tl. This substitution is confirmed by XAS data, showing the presence of Tl+ having a first coordination shell mainly formed by 6 O atoms at 2.84(2) Å. Voltaite occurs as dark green cubic crystals, up to 1 mm in size. Voltaite is chemically zoned, with distinct domains having chemical formula and respectively. Infrared spectroscopy confirmed the occurrence of minor also in voltaite. Its unit-cell parameter is a = 27.2635 Å, V = 20265(4) Å3, space group The crystal structure was refined down to R1 = 0.0434 for 817 reflections with Fo > 4σ(Fo) and 87 refined parameters. The partial replacement of K by Tl is confirmed by the structural refinement. XAS spectroscopy showed that Tl+ is bonded to six O atoms, at 2.89(2) Å. The multi-technique characterization of thallium-bearing alum-(K) and voltaite improves our understanding of the role of K-bearing sulfates in immobilizing Tl in acid mine drainage systems, temporarily avoiding its dispersion in the environment.
Electronic states of iron in the lower mantle’s dominant mineral, (Mg,Fe,Al)(Fe,Al,Si)O3 bridgmanite, control physical properties of the mantle including density, elasticity, and electrical and thermal conductivity. However, the determination of electronic states of iron has been controversial, in part due to different interpretations of Mössbauer spectroscopy results used to identify spin state, valence state, and site occupancy of iron. We applied energy-domain Mössbauer spectroscopy to a set of four bridgmanite samples spanning a wide range of compositions: 10–50% Fe/total cations, 0–25% Al/total cations, 12–100% Fe3+/total Fe. Measurements performed in the diamond-anvil cell at pressures up to 76 GPa below and above the high to low spin transition in Fe3+ provide a Mössbauer reference library for bridgmanite and demonstrate the efects of pressure and composition on electronic states of iron. Results indicate that although the spin transition in Fe3+ in the bridgmanite B-site occurs as predicted, it does not strongly affect the observed quadrupole splitting of 1.4 mm/s, and only decreases center shift for this site to 0 mm/s at ~70 GPa. Thus center shift can easily distinguish Fe3+ from Fe2+ at high pressure, which exhibits two distinct Mössbauer sites with center shift ~1 mm/s and quadrupole splitting 2.4–3.1 and 3.9 mm/s at ~70 GPa. Correct quantification of Fe3+/total Fe in bridgmanite is required to constrain the efects of composition and redox states in experimental measurements of seismic properties of bridgmanite. In Fe-rich, mixed-valence bridgmanite at deep-mantle-relevant pressures, up to ~20% of the Fe may be a Fe2.5+ charge transfer component, which should enhance electrical and thermal conductivity in Fe-rich heterogeneities at the base of Earth’s mantle.