| 1. |
- Altieri, Alessandra, et al.
(författare)
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Blue growth zones caused by Fe2+ in tourmaline crystals from the San Piero in Campo gem-bearing pegmatites, Elba Island, Italy
- 2022
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Ingår i: Mineralogical magazine. - : Mineralogical Society. - 0026-461X .- 1471-8022. ; 86:6, s. 910-919
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Tidskriftsartikel (refereegranskat)abstract
- Two tourmaline crystals with a blue growth zone at the analogous pole, respectively from the San Silvestro and the Fucili pegmatites, located in the San Piero in Campo village, Elba Island (Tyrrhenian Sea, Italy), have been described for the first time using compositional and spectroscopic data to define their crystal-chemical aspects and the causes of the colour. Compositional data obtained by electron microprobe analysis indicate that both tourmalines belong to the elbaite–fluor-elbaite series. The upper part of each crystal is characterised by an increased amount of Fe (FeO up to ~1 wt.%) and a Ti content below the detection limit. Optical absorption spectra recorded on the blue zone of both samples show absorption bands caused by spin-allowed d-d transitions in [6]-coordinated Fe2+, and no intervalence charge transfer Fe2+-Ti interactions, indicating that Fe2+ is the only chromophore. Mössbauer analysis of the blue zone of the Fucili sample confirmed the Fe2+ oxidation state, implying that the redox conditions in the crystallisation environment were relatively reducing. The presence of colour changes at the analogous termination during tourmaline crystal growth suggests a change in the composition of the crystallisation environment, probably associated with a partial opening of the system.
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| 2. |
- Altieri, Alessandra, et al.
(författare)
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Dark-coloured Mn-rich overgrowths in an elbaitic tourmaline crystal from the Rosina pegmatite, San Piero in Campo, Elba Island, Italy: witness of late-stage opening of the geochemical system
- 2023
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Ingår i: Mineralogical magazine. - : Mineralogical Society. - 0026-461X .- 1471-8022. ; 87:1, s. 130-142
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Tidskriftsartikel (refereegranskat)abstract
- Multicoloured tourmalines from Elba Island, commonly display dark-coloured terminations due to incorporation of Fe, and also occasionally Mn. The mechanisms which led to the availability of these elements in the late-stage residual fluids are not yet completely understood. For this purpose, we investigated a representative tourmaline crystal found naturally in two fragments within a wide miarolitic cavity in the Rosina pegmatite (San Piero in Campo, Elba Island, Italy), and characterised by late-stage dark-coloured overgrowths. Microstructural and paragenetic observations, together with compositional and spectroscopic data (electron microprobe and optical absorption spectroscopy), provide evidence which shows that the formation of the dark-coloured Mn-rich overgrowths are the result of a pocket rupture. This event caused alteration of the cavity-coating spessartine garnet by highly-reactive late-stage cavity fluids by leaching processes, with the subsequent release of Mn to the residual fluids. We argue that the two fragments were originally a single crystal, which underwent natural breakage followed by the simultaneous growth of Mn-rich dark terminations at both breakage surfaces. This conclusion supports the evidence for a pocket rupture event, responsible for both the shattering of the tourmaline crystal and the compositional variation of the cavity-fluids related to the availability of Mn, which was incorporated by the tourmaline crystals. Additionally, a comparison of the dark overgrowths formed at the analogous and the antilogous poles, provides information on tourmaline crystallisation at the two different poles. The antilogous pole is characterised by a higher affinity for Ca, F and Ti, and a selective uptake of Mn2+, even in the presence of a considerable amount of Mn3+ in the system. This uneven uptake of Mn ions resulted in the yellow–orange colouration of the antilogous overgrowth (Mn2+ dependent) rather than the purple-reddish colour of the analogous overgrowths (Mn3+ dependent).
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| 7. |
- Biagion, Cristian, et al.
(författare)
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The crystal structure of turneaureite, Ca5(AsO4)3Cl, the arsenate analog of chlorapatite and its relationships with the arsenate apatites johnbaumite and svabite
- 2017
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Ingår i: American Mineralogist. - : Mineralogical Society of America. - 0003-004X .- 1945-3027. ; 102, s. 1981-1986
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Tidskriftsartikel (refereegranskat)abstract
- The crystal structure of turneaureite, ideally Ca5(AsO4)3Cl, was studied using a specimen from the Brattfors mine, Nordmark, Värmland, Sweden, by means of single-crystal X-ray diffraction data. The structure was refinedto R1 = 0.017 on the basis of 716 unique reflectios with Fo > 4σ(Fo) in the P63/m space group, with unit-cell parameters a = 9.9218(3), c = 6.8638(2) Å, V = 585.16(4) Å3. The chemical composition of the sample, determined by electron-microprobe analysis, is (in wt%; average of 10 spot analyses): SO3 0.22, P2O5 0.20, V2O5 0.01, As2O5 51.76, SiO2 0.06, CaO 41.39, MnO 1.89, SrO 0.12, BaO 0.52, PbO 0.10, Na2O 0.02, F 0.32, Cl 2.56, H2Ocalc 0.58, O(≡F+Cl) –0.71, total 99.04. On the basis of 13 anions per formula unit, the empirical formula corresponds to (Ca4.82Mn0.17Ba0.02Sr0.01)∑5.02 (As2.94P0.02S0.02Si0.01)∑2.99O12[Cl0.47(OH)0.42F0.11]∑1.00.Turneaureite is topologically similar to the other members of the apatite supergroup: columns of face-sharing M1 polyhedra running along c are connected through TO4 tetrahedra with channels hosting M2 cations and X anions. Owing to its particular chemical composition, the studied turneaureite can be considered as a ternary calcium arsenate apatite; consequently it has several partially filledanion sites within the anion columns. Polarized single-crystal FTIR spectra of the studied sample indicate stronger hydrogen bonding and less diverse short-range atom arrangements around (OH) groups in turneaureite as compared to the related minerals johnbaumite and svabite. An accurate knowledge of the atomic arrangement of this apatite-remediation mineral represents an improvement in our understanding of minerals able to sequester and stabilize heavy metals such as arsenic in polluted areas.
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| 8. |
- Biagioni, Cristian, et al.
(författare)
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Bianchiniite, Ba2(Ti4+V3+)(As2O5)2OF, a new diarsenite mineral fromthe Monte Arsiccio mine, Apuan Alps, Tuscany, Italy
- 2021
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Ingår i: Mineralogical magazine. - : Mineralogical Society. - 0026-461X .- 1471-8022. ; 3, s. 354-363
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Tidskriftsartikel (refereegranskat)abstract
- The new mineral bianchiniite, Ba2(Ti4+V3+)(As2O5)2OF, has been discovered in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. It occurs as brown {001} tabular crystals, up to 1 mm across, with a vitreous lustre. It is brittle, with a perfect {001} cleavage. Streak is brownish. In reflected light, bianchiniite is grey, with orange–yellow internal reflections. It is weakly bireflectant, with a very weak anisotropy in shades of grey. Minimum and maximum reflectance data for COM wavelengths [Rmin/Rmax (%), (λ, nm)] are: 5.0/5.8 (470),5.7/6.5 (546), 5.7/7.0 (589) and 5.2/6.3 (650). Electron microprobe analyses gave (wt.% – average of 10 spot analyses): TiO2 10.34, V2O33.77, Fe2O3 3.76,As2O3 44.36, Sb2O3 0.22, SrO 0.45, BaO 34.79, PbO 0.28, F 1.77, sum 99.74, –O=F–0.75, total 98.99. On the basis of 12 anions per formula unit, the empirical formula of bianchiniite is (Ba2.00Sr0.04Pb0.02)Σ2.06(Ti4+1.14V3+0.44Fe3+0.42)Σ2.00[(As3.96Sb0.02)Σ3.98O10](O1.18F0.82)Σ2.00. Bianchiniite is tetragonal, space group I4/mcm, with unit-cell parameters a = 8.7266(4), c = 15.6777(7) Å, V = 1193.91(12) Å3 and Z = 8. Its crystal structure was refined from single-crystal X-ray diffraction data to R1 = 0.0134 on the basis of 555 unique reflections with Fo > 4σ(Fo)and 34 refined parameters. The crystal structure shows columns of corner-sharing [Ti/(V,Fe)]-centred octahedra running along c, connected along a and b through (As2O5) dimers. A {001} layer of Ba-centred [10+2]-coordinated polyhedra is intercalated between (As2O5) dimers. Bianchiniite has structural relations with fresnoite- and melilite-group minerals. The name honours the two mineral collectors Andrea Bianchini (b. 1959) and Mario Bianchini (b. 1962) for their contribution to the knowledge of the mineralogy of pyrite ± baryte ± iron-oxide ore deposits from the Apuan Alps.
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| 10. |
- Biagioni, Cristian, et al.
(författare)
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The crystal structure of svabite, Ca5(AsO4)3F, an arsenate member of the apatite supergroup
- 2016
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Ingår i: American Mineralogist. - : Mineralogical Society of America. - 0003-004X .- 1945-3027. ; 101, s. 1750-1755
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Tidskriftsartikel (refereegranskat)abstract
- The crystal structure of svabite, ideally Ca5(AsO4)3F, was studied using a specimen from the Jakobsberg mine, Värmland, Sweden, by means of single-crystal X‑ray diffraction data. The structure was refined to R1 = 0.032 on the basis of 928 unique reflections with Fo > 4s(Fo) in the P63/m space group, with unit-cell parameters a = 9.7268(5), c = 6.9820(4) Å, V = 572.07(5) Å3. The chemical composition of the sample, determined by electron-microprobe analysis, is (in wt%, average of 10 spot analyses): SO3 0.49, P2O5 0.21, V2O5 0.04, As2O5 51.21, SiO2 0.19, CaO 39.31, MnO 0.48, SrO 0.03, PbO 5.19, Na2O 0.13, F 2.12, Cl 0.08, H2Ocalc 0.33, O (≡ F+Cl) –0.91, total 98.90. On the basis of 13 anions per formula unit, the empirical formula corresponds to (Ca4.66Pb0.16Mn0.04Na0.03)Σ4.89(As2.96S0.04Si0.02P0.02)Σ3.04O12[F0.74(OH)0.24Cl0.01]. Svabite is topologically similar to the other members of the apatite supergroup: columns of face-sharing M1 polyhedra running along c are connected through TO4 tetrahedra with channels hosting M2 cations and X anions. The crystal structure of synthetic Ca5(AsO4)3F was previously reported as triclinic. On the contrary, the present refinement of the crystal structure of svabite shows no deviations from the hexagonal symmetry. An accurate knowledge of the atomic arrangement of this apatite-remediation mineral represents an improvement in our understanding of minerals able to sequester and stabilize heavy metals such as arsenic in polluted areas.
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| 16. |
- Bosi, Ferdinando, et al.
(författare)
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Crystal-chemical aspects of the roméite group, A2Sb2O6Y, of the pyrochlore supergroup
- 2017
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Ingår i: Mineralogical magazine. - : Mineralogical Society. - 0026-461X .- 1471-8022. ; 81:6, s. 1287-1302
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Tidskriftsartikel (refereegranskat)abstract
- Four specimens of the roméite-group minerals oxyplumboroméite and fluorcalcioroméite from the Långban Mn-Fe deposit in Central Sweden were structurally and chemically characterized by single-crystal X-ray diffraction, electron microprobe analysis and infrared spectroscopy. The data obtained and those on additional roméite samples from literature show that the main structural variations within the roméite group are related to variations in the content of Pb2+, which is incorporated into the roméite structure via the substitution Pb2+ → A2+ where A2+ = Ca, Mn and Sr. Additionally, the cation occupancy at the six-fold coordinated B site, which is associated with the heterovalent substitution BFe3+ + Y□ → BSb5+ + YO2–, can strongly affect structural parameters.Chemical formulae of the roméite minerals group are discussed. According to crystal-chemical information, the species associated with the name ‘kenoplumboroméite’, hydroxycalcioroméite and fluorcalcioroméite most closely approximate end-member compositions Pb2(SbFe3+)O6□, Ca2(Sb5+Ti)O6(OH) and (CaNa)Sb2O6F, respectively. However, in accord with pyrochlore nomenclature rules, their names correspond to multiple end-members and are best described by the general formulae: (Pb,#)2(Sb,#)2O6□, (Ca,#)2(Sb,#)2O6(OH) and (Ca,#)Sb2(O,#)6F, where ‘#’ indicates an unspecified charge-balancing chemical substituent, including vacancies.
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| 19. |
- Bosi, Ferdinando, et al.
(författare)
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Crystal chemistry of spinels in the system MgAl2O4-MgV2O4-Mg2VO4
- 2016
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Ingår i: American Mineralogist. - : Mineralogical Society of America. - 0003-004X .- 1945-3027. ; 101, s. 580-586
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Tidskriftsartikel (refereegranskat)abstract
- Eight spinel single-crystal samples belonging to the spinel sensu stricto-magnesiocoulsonite series (MgAl2O4-MgV2O4) were synthesized and crystal-chemically characterized by X‑ray diffraction, electron microprobe and optical absorption spectroscopy. Site populations show that the tetrahedrally coordinated site (T) is populated by Mg and minor Al for the spinel sensu stricto compositions, and only by Mg for the magnesiocoulsonite compositions, while the octahedrally coordinated site (M) is populated by Al, V3+, minor Mg, and very minor amounts of V4+. The latter occurs in appreciable amounts in the Al-free magnesium vanadate spinel, T(Mg)M(Mg0.26V3+1.48V4+0.26)O4, showing the presence of the inverse spinel VMg2O4. The studied samples are characterized by substitution of Al3+ for V3+ and (Mg2++V4+) for 2V3+ described in the system MgAl2O4-MgV2O4-VMg2O4.The present data in conjunction with data from the literature provide a basis for quantitative analyses of two solid-solution series MgAl2O4-MgV23+O4 and MgV23+O4-V4+Mg2O4. Unit-cell parameter increases with increasing V3+ along the series MgAl2O4-MgV2O4 (8.085–8.432 Å), but only slightly increases with increasing V3+ along the series VMg2O4-MgV2O4 (8.386–8.432 Å). Although a solid solution could be expected between the MgAl2O4 and VMg2O4 end-members, no evidence was found. Amounts of V4+ are nearly insignificant in all synthetic Al-bearing vanadate spinels, but are appreciable in Al-free vanadate spinel.An interesting observation of the present study is that despite the observed complete solid-solution along the MgAl2O4-MgV2O4 and MgV2O4-VMg2O4 series, the spinel structure seems to be unable to stabilize V4+ in any intermediate members on the MgAl2O4-Mg2VO4 join even at high oxygen fugacities. This behavior indicates that the accommodation of specific V-valences can be strongly influenced by crystal-structural constraints, and any evaluation of oxygen fugacities during mineral formation based exclusively on V cation valence distributions in spinel should be treated with caution. The present study underlines that the V valency distribution in spinels is not exclusively reflecting oxygen fugacities, but also depends on activities and solubilities of all chemical components in the crystallization environment.
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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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