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| 24. |
- Bosi, Ferdinando, et al.
(författare)
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Experimental cation redistribution in the tourmaline lucchesiite, CaFe2+3Al6(Si6O18)(BO3)3(OH)3O
- 2018
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Ingår i: Physics and chemistry of minerals. - : Springer Science and Business Media LLC. - 0342-1791 .- 1432-2021. ; 45:7, s. 621-632
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Tidskriftsartikel (refereegranskat)abstract
- Natural Mg-rich lucchesiite was thermally treated in air and hydrogen atmosphere up to 800 °C to study potential changes in Fe-, Mg- and Al ordering over the octahedrally coordinated Y- and Z -sites, and to explore possible applications to intracrystalline geothermometry based on tourmaline. Overall, the experimental data (structural refinement, Mössbauer, infrared and optical absorption spectroscopy) show that thermal treatment of lucchesiite results in an increase of Fetot contents at Z balanced by an increase of Mg and Al at Y . This process is accompanied by a significant deprotonation of the O3 anion site. The Fe order–disorder reaction depends more on temperature, than on redox conditions. During heat treatment in H2 ,reduction of Fe3+ to Fe2+ was not observed despite strongly reducing conditions, indicating that the fO2 conditions do not exclusively control the Fe oxidation state at the present experimental conditions. On the basis of this and previous studies, the intersite order–disorder process induced by thermal treatment indicates that Fe redistribution is an important factor for Fe–Mg–Al-exchange and is significant at temperatures around 800 °C. As a result, Fe–Mg–Al intersite order–disorder is sensitive to temperature variations, whereas geothermometers based solely on Mg–Al order–disorder appear insensitive and involve large uncertainties. The presented findings are important for interpretation of the post-crystallization history of both tourmaline and tourmaline host rocks, and indicate that successful tourmaline geothermometers may be developed by thermal calibration of the Fe-Mg–Al order–disorder reaction.
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| 25. |
- Bosi, Ferdinando, et al.
(författare)
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Experimental evidence for partial Fe2+ disorder at the Y and Z sites of tourmaline: a combined EMP, SREF, MS, IR and OAS study of schorl
- 2015
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Ingår i: Mineralogical magazine. - : Mineralogical Society. - 0026-461X .- 1471-8022. ; 79:3, s. 515-528
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Tidskriftsartikel (refereegranskat)abstract
- An experimental study of an Al-rich schorl sample from Cruzeiro mine (Minas Gerais, Brazil) was carried out using electron microprobe analysis, structural refinement and Mössbauer, infrared and optical absorption spectroscopy in order to explore the disordering of Fe2+ over the Y and Z sites of the tourmaline structure.A structural formula was obtained by merging chemical and structural data. The cation distribution at the two non-equivalent octahedrally coordinated sites (Y and Z) was obtained by two different optimization procedures which, minimizing the residuals between observed and calculated data, converged to the formula: X(Na0.65〈0.32Ca0.02K0.01)Σ1.00Y(Fe1.652+Al1.15Fe0.063+Mn0.052+Zn0.05Ti0.044+)Σ3.00Z(Al5.52Fe0.302+Mg0.18)Σ6.00[T(Si5.87Al0.13)Σ6.00O18](BBO3)3V(OH)3W[(OH)0.34F0.28O0.38]Σ1.00.This result shows a partial disordering of Fe2+ over the Y and Z sites which explains adequately the mean atomic number observed for the Z site (13.5±0.1). Such a disordering is also in line with the shoulder recorded in the Mössbauer spectrum (fitted by a doublet with isomer shift of 1.00 mm/s and quadrupole splitting of 1.38 mm/s) as well as with the asymmetric bands recorded in the optical absorption spectrum at ∼9000 and 14,500 cm–1 (modelled by four Gaussian bands, centred at 7677 and 9418 cm–1, and 13,154 and 14,994 cm–1, respectively).The high degree of consistency in the results obtained using the different methods suggests that the controversy over Fe2+ order can be ascribed to the failure to detect small amounts of Fe2+ at Z (typically <<10% atoms/site) rather than a steric effect of Fe2+ on the tourmaline structure.
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| 26. |
- Bosi, Ferdinando, et al.
(författare)
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Late magmatic controls on the origin of schorlitic and foititic tourmalines from late-Variscan peraluminous granites of the Arbus pluton (SW Sardinia, Italy) : Crystal-chemical study and petrological constraints
- 2018
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Ingår i: Lithos. - : Elsevier BV. - 0024-4937 .- 1872-6143. ; 308-309, s. 395-411
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Tidskriftsartikel (refereegranskat)abstract
- Tourmalines from the late-Variscan Arbus pluton (SW Sardinia) and its metamorphic aureole were structurally and chemically characterized by single-crystal X-ray diffraction, electron and nuclear microprobe analysis, Mössbauer, infrared and optical absorption spectroscopy, to elucidate their origin and relationships with the magmatic evolution during the pluton cooling stages. The Arbus pluton represents a peculiar shallow magmatic system, characterized by sekaninaite (Fe-cordierite)-bearing peraluminous granitoids, linked via AFC processes to gabbroic mantle-derived magmas. The Fe2+-Al-dominant tourmalines occur in: a) pegmatitic layers and pods, as prismatic crystals; b) greisenized rocks and spotted granophyric dikes, as clots or nests of fine-grained crystals in small miaroles locally forming orbicules; c) pegmatitic veins and pods close to the contacts within the metamorphic aureole. Structural formulae indicate that tourmaline in pegmatitic layers is schorl, whereas in greisenized rocks it ranges from schorl to fluor-schorl. Tourmalines in thermometamorphosed contact aureole are schorl, foitite and Mg-rich oxy-schorl. The main substitution is Na + Fe2+ ↔ □ + Al, which relates schorl to foitite. The homovalent substitution (OH) ↔ F at the O1 crystallographic site relates schorl to fluor-schorl, while the heterovalent substitution Fe2+ + (OH, F) ↔ Al + O relates schorl/fluor-schorl to oxy-schorl. Tourmaline crystallization in the Arbus pluton was promoted by volatile (B, F and H2O) enrichment, low oxygen fugacity and Fe2+ activity. The mineralogical evolutive trend is driven by decreasing temperature, as follows: sekaninaite + quartz → schorl + quartz → fluor-schorl + quartz → foitite + quartz. The schorl → foitite evolution represents a distinct trend towards (Al + □) increase and unit-cell volume decrease. These trends are typical of granitic magmas and consistent with Li-poor granitic melts, as supported by the absence of elbaite and other Li-minerals in the Arbus pluton. Tourmaline-bearing rocks reflect the petrogenetic significance of contribution from a metapelitic crustal component during the evolution of magmas in the middle-upper crust.
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| 27. |
- Bosi, Ferdinando, et al.
(författare)
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Lowering R3m Symmetry in Mg-Fe-Tourmalines: The Crystal Structures of Triclinic Schorl and Oxy-Dravite, and the Mineral luinaite-(OH) Discredited
- 2022
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Ingår i: Minerals. - : MDPI AG. - 2075-163X. ; 12:4, s. 1-10
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Tidskriftsartikel (refereegranskat)abstract
- Discreditation of the monoclinic tourmaline mineral species luinaite-(OH), ideally (Na,▯)(Fe2+,Mg)3Al6(BO3)3Si6O18(OH)4 was approved by the IMA-CNMNC (proposal 21-L) and is described. We analyzed two luinaite-(OH) samples: one from the type locality Cleveland tin mine, Luina, Waratah, Tasmania, Australia, and the other from Blue Mountain Saddle (Bald Hornet Claim), North Bend, King County, Washington, DC, USA. Biaxial (−) crystals representative of the studied samples were spectroscopically (Mössbauer, polarized Fourier transform infrared, optical absorption spectroscopy), chemically (nuclear microprobe analysis and electron microprobe analysis), and structurally characterized (single-crystal X-ray diffraction). Results show the occurrence of a triclinic structure for the studied luinaite-(OH) samples, which differs only in terms of a slight structural distortion from typical trigonal tourmaline structure (the topology of the structure is retained). As a result, following the IMA-CNMNC and tourmaline nomenclature rules, the triclinic luinaite-(OH) from the type locality (Australia) can be considered as the triclinic dimorph of schorl, as its chemical composition corresponds to schorl, and thus it should be referred as schorl-1A. Similarly, the triclinic sample from the USA can be considered as the triclinic dimorph of oxy-dravite, as its chemical composition corresponds to oxy-dravite, and then is referred to as oxy-dravite-1A.
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| 28. |
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| 29. |
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| 30. |
- Bosi, Ferdinando, et al.
(författare)
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Mn-bearing purplish-red tourmaline from the Anjanabonoina pegmatite, Madagascar
- 2021
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Ingår i: Mineralogical magazine. - : Mineralogical Society. - 0026-461X .- 1471-8022. ; 85:2, s. 242-253
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Tidskriftsartikel (refereegranskat)abstract
- A gem-quality purplish-red tourmaline sample of alleged liddicoatitic composition from the Anjanabonoina pegmatite, Madagascar, hasbeen fully characterised using a multi-analytical approach to define its crystal-chemical identity. Single-crystal X-ray diffraction, chem-ical and spectroscopic analysis resulted in the formula: X(Na0.41□0.35Ca0.24)Σ1.00Y(Al1.81Li1.00Fe3+0.04Mn3+0.02Mn2+0.12Ti0.004)Σ3.00ZAl6[T(Si5.60B0.40)Σ6.00O18](BO3)3(OH)3W[(OH)0.50F0.13O0.37]Σ1.00, which corresponds to the tourmaline species elbaite having the typical space group R3m and relatively small unit-cell dimensions, a= 15.7935(4) Å, c= 7.0860(2) Å and V= 7.0860(2) Å3.Optical absorption spectroscopy showed that the purplish-red colour is caused by minor amounts of Mn3+(Mn2O3= 0.20 wt.%).Thermal treatment in air up to 750°C strongly intensified the colour of the sample due to the oxidation of all Mn2+ to Mn3+ (Mn2O3 up to 1.21 wt.%). Based on infrared and Raman data, a crystal-chemical model regarding the electrostatic interaction betweenthe X cation and W anion, and involving the Y cations as well, is proposed to explain the absence or rarity of the mineral species ‘liddicoatite’.
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