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- Ardit, Matteo, et al.
(författare)
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Vanadium-induced coloration in grossite (CaAl4O7) and hibonite (CaAl12O19)
- 2021
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Ingår i: American Mineralogist. - : Mineralogical Society of America. - 0003-004X .- 1945-3027. ; 106:4, s. 599-608
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Tidskriftsartikel (refereegranskat)abstract
- High concentrations of vanadium cause very unusual coloration in hibonite (purple) and grossite (light violet) crystals in an exotic mineral assemblage from Sierra de Comechingones (Argentina). In the hibonite (CaAl12O19) structure vanadium ions, in various valence states (divalent, trivalent, and tetravalent), may be distributed over five crystallographic sites with coordinations corresponding to different polyhedra, namely, three unequal octahedra [M1 (D3d), M4 (C3ν), and M5 (Cs)], one M3 tetrahedron (C3ν), and one unusual fivefold-coordinated trigonal bipyramid M2 (D3h). Possible locations of vanadium ions in grossite (CaAl4O7) are limited to two crystallographically distinct sites (T1 and T2, both C1) in tetrahedral coordination.The combination of single-crystal X-ray diffraction and absorption spectroscopy techniques aided by chemical analyses has yielded details on the nature of the vanadium-induced color in both hibonite and grossite crystals. In hibonite, both M4 face-sharing octahedral and M2 trigonal bipyramid sites of the R-block are partially occupied by V3+. Strongly polarized bands recorded at relatively low energies in optical absorption spectra indicate that V2+ is located at the M4 octahedral site of the hibonite R-block. Chemical analyses coupled with an accurate determination of the electron densities at structural sites in hibonite suggest that the vanadium ions occupy about 10 and 5% of the M4 and M2 sites, respectively. For grossite, polarized optical absorption spectra reveal no indications of V2+; all observed absorption bands can be assigned to V3+ in tetrahedral coordination. Although not evident by the observed electron densities at the T sites of grossite (due to the low-V content), longer bond distances, and a higher degree of polyhedral distortion suggest that V3+ is located at the T2 site.
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| 3. |
- Fu, Jie, et al.
(författare)
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Density and sound velocity of liquid Fe-S alloys at Earth's outer core P-T conditions
- 2020
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Ingår i: American Mineralogist. - : MINERALOGICAL SOC AMER. - 0003-004X .- 1945-3027. ; 105:9, s. 1349-1354
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Tidskriftsartikel (refereegranskat)abstract
- Pressure-temperature-volume (P-T-V) data on liquid iron-sulfur (Fe-S) alloys at the Earth's outer core conditions (similar to 136 to 330 GPa, similar to 4000 to 7000 K) have been obtained by first-principles molecular dynamics simulations. We developed a thermal equation of state (EoS) composed of Murnaghan and Mie-Gruneisen-Debye expressions for liquid Fe-S alloys. The density and sound velocity are calculated and compared with Preliminary Reference Earth Model (PREM) to constrain the S concentration in the outer core. Since the temperature at the inner core boundary (TICB) has not been measured precisely (4850 similar to 7100 K), we deduce that the S concentration ranges from 10 similar to 14 wt% assuming S is the only light element. Our results also show that Fe-S alloys cannot satisfy the seismological density and sound velocity simultaneously and thus S element is not the only light element. Considering the geophysical and geochemical constraints, we propose that the outer core contains no more than 3.5 wt%S, 2.5 wt%O, or 3.8 wt% Si. In addition, the developed thermal EoS can be utilized to calculate the thermal properties of liquid Fe-S alloys, which may serve as the fundamental parameters to model the Earth's outer core.
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| 4. |
- Scribner, Emily D., et al.
(författare)
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Magnesio-lucchesiite, CaMg3Al6(Si6O18)(BO3)3(OH)3O, a new species of the tourmaline supergroup
- 2021
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Ingår i: American Mineralogist. - : Mineralogical Society of America. - 0003-004X .- 1945-3027. ; 106:6, s. 862-871
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Tidskriftsartikel (refereegranskat)abstract
- Magnesio-lucchesiite, ideally CaMg3Al6(Si6O18)(BO3)3(OH)3O, is a new mineral species of the tourmaline supergroup. The holotype material was discovered within a lamprophyre dike that cross-cuts tourmaline-rich metapelites within the exocontact of the O’Grady Batholith, Northwest Territories (Canada). Two additional samples were found at San Piero in Campo, Elba Island, Tuscany (Italy) in hydrothermal veins embedded in meta-serpentinites within the contact aureole of the Monte Capanne intrusion. The studied crystals of magnesio-lucchesiite are black in a hand sample with vitreous luster, conchoidal fracture, an estimated hardness of 7–8, and a calculated density of 3.168 (Canada) and 3.175 g/cm3 (Italy). In plane-polarized light, magnesio-lucchesiite is pleochroic (O = dark brown, E = colorless) and uniaxial (–); its refractive index values are nω = 1.668(3) and nε = 1.644(3) (Canada), and nω = 1.665(5) and nε = 1.645(5) (Italy). Magnesio-lucchesiite is trigonal, space group R3m, Z = 3, with a = 15.9910(3) Å, c = 7.2224(2) Å, V = 1599.42(7) Å3 (Canada) and with a = 15.9270(10) Å, c = 7.1270(5) Å, V = 1565.7(2) Å3 (Italy, sample 1). The crystal structure of magnesio-lucchesiite was refined to R1 = 3.06% using 2953 reflections with Fo > 4σ(Fo) (Canadian sample; 1.96% / 1225 for the Italian sample) The Canadian (holotype) sample has the ordered empirical formula X(Ca0.60Na0.39K0.01)Σ1.00Y(Mg2.02Fe2+0.62Fe3+0.09Ti0.25V0.01Cr0.01)Σ3.00Z(Al5.31Fe3+0.69)Σ6.00[T(Si5.98Al0.02)Σ6.00O18(BO3)3V[(OH)2.59O0.41]Σ3.00W(O0.78F0.22)Σ1.00. The Italian (co-type) material shows a wider chemical variability, with two different samples from the same locality having ordered chemical formulas: X(Ca0.88Na0.12)Σ1.00Y(Mg1.45Fe2+0.40Al0.79Fe3+0.36)Σ3.00ZAl6[T(Si5.05Al0.95)Σ6.00O18](BO3)3V[(OH)2.90O0.10]Σ3.00W(O0.98F0.02)Σ1.00(sample 1) and X(Ca0.71Na0.21o0.08)Σ1.00Y(Mg2.49Fe2+0.41Ti0.10)Σ3.00Z(Al5.44Fe3+0.46Mg0.09V0.01)Σ6.00[T(Si5.87Al0.13)Σ6.00O18](BO3)3V(OH)3W[O0.61(OH)0.39]Σ1.00 (sample 2). Magnesio-lucchesiite is an oxy-species belonging to the calcic group of the tourmaline supergroup. It is related to lucchesiite by the homovalent substitution YFe ↔ YMg, and to feruvite by the homovalent and heterovalent substitutions YFe ↔ YMg and ZAl3+ + WO2– ↔ ZMg2+ + W(OH)1–. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2019-025). Occurrences of magnesio-lucchesiite show that its presence is not restricted to replacement of mafic minerals only; it may also form in metacarbonate rocks by fluctuations of F and Al during crystallization of common uvitic tourmaline. High miscibility with other tourmaline end-members indicates the large petrogenetic potential of magnesio-lucchesiite in Mg,Al-rich calc-silicate rocks, as well as contact-metamorphic and metasomatic rocks.
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| 5. |
- Sordyl, Julia, et al.
(författare)
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Single-crystal analysis of La-doped pyromorphite [Pb5(PO4)3Cl]
- 2023
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Ingår i: American Mineralogist. - : Mineralogical Society of America. - 0003-004X .- 1945-3027. ; 108:12, s. 2323-2330
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Tidskriftsartikel (refereegranskat)abstract
- Rare earth elements (REE) in calcium apatite have been widely described in the literature. Based on the investigations of minerals and their synthetic analogs, the mechanism of substitution of REE3+ for Ca2+ and their structural positions are well established. Although the presence of REE in natural pyromorphite has been reported, the structural response of substitution of REE3+ for Pb2+ is not established. A better understanding of REE-rich Pb-apatite may facilitate the potential use of this mineral in industrial processes. Two La-doped pyromorphite analogs [Pb5(PO4)3Cl] and two control pyromorphite analogs (with the absence of La) were synthesized from aqueous solutions at 25 degrees C. Na+ and K+ were used as charge-compensating ions to facilitate the incorporation of trivalent REE cations (La3+ + Na+ ↔ 2Pb2+ and La3+ + K+ ↔ 2Pb2+). Microprobe analysis, scanning electron microscopy, and Raman spectroscopy were used to confirm the purity of obtained phases. High-precision crystal structure refinements (R1 = 0.0140-0.0225) of all four compounds were performed from single-crystal X-ray diffraction data. The La content varied from 0.12(1) to 0.19(1) atoms per formula unit with the counter ions of K+ and Na+, respectively. Both substituting ions were accommodated at the Pb1 site only. By comparing the La-doped pyromorphite analogs with their control samples, it was possible to detect small changes in bond distances and polyhedral volumes caused by the La substitution. Variations in individual and mean interatomic distances reflected the cumulative effect of both the amount of substitution and ionic radii of substituting ions (La3+, Na+, and K+).
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