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1.
  • Bosi, Ferdinando, et al. (författare)
  • Experimental cation redistribution in the tourmaline lucchesiite, CaFe2+3Al6(Si6O18)(BO3)3(OH)3O
  • 2018
  • Ingår i: Physics and chemistry of minerals. - 0342-1791. ; 45:7, s. 621-632
  • 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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2.
  • Bosi, Ferdinando, et al. (författare)
  • 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
  • Ingår i: Lithos. - Elsevier. - 0024-4937. ; 308-309, s. 395-411
  • 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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3.
  • Gori, Claudia, et al. (författare)
  • Co2+-doped diopside: crystal structure and optical properties
  • 2018
  • Ingår i: Physics and chemistry of minerals. - 0342-1791. ; 45:5, s. 443-461
  • Tidskriftsartikel (refereegranskat)abstract
    • Synthetic clinopyroxenes along the CaMgSi2O6– CaCoSi2O6 join were investigated by a combined chemical-structuralspectroscopic approach. Single crystals were synthesized by flux growth methods, both from Ca-saturated and Ca-deficient starting compositions. Single crystal structure refinements show that the incorporation of Co2+ at the octahedrally coordinated cation sites of diopside, increases the unit-cell as well as the M1 and the M2 polyhedral volumes. Spectroscopic investigations (UV–VIS–NIR) of the Ca-rich samples reveal three main optical absorption bands, i.e. 4T1g → 4T2g(F), 4T1g → 4A2g(F) and 4T1g → 4T1g(P) as expected for Co2+ at a six-coordinated site. The bands arising from the 4T1g → 4T2g(F) and the 4T1g → 4T1g(P) electronic transitions, are each split into two components, due to the distortions of the M1 polyhedron from ideal Oh- symmetry. In spectra of both types, a band in the NIR range at ca 5000 cm−1 is caused by the 4A2g → 4T1g(F) electronic transition in Co2+ in a cubic field in the M2 site. Furthermore, an additional component to a band system at 14,000 cm−1, due to electronic transitions in Co2+ at the M2 site, is recorded in absorption spectra of Ca-deficient samples. No variations in Dq and Racah B parameters for Co2+ at the M1 site in response to compositional changes, were demonstrated, suggesting complete relaxation of the M1 polyhedron within the CaMgSi2O6– CaCoSi2O6 solid solution.
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  • Biagion, Cristian, et al. (författare)
  • The crystal structure of turneaureite, Ca5(AsO4)3Cl, the arsenate analog of chlorapatite and its relationships with the arsenate apatites johnbaumite and svabite
  • 2017
  • Ingår i: American Mineralogist. - 0003-004X. ; 102, s. 1981-1986
  • 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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7.
  • Bosi, Ferdinando, et al. (författare)
  • Crystal-chemical aspects of the roméite group, A2Sb2O6Y, of the pyrochlore supergroup
  • 2017
  • Ingår i: Mineralogical magazine. - 0026-461X. ; 81:6, s. 1287-1302
  • 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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  • Bosi, Ferdinando, et al. (författare)
  • Oxy-foitite, □(Fe2+Al2)Al6(Si6O18)(BO3)3(OH)3O, a new mineral species of the tourmaline supergroup
  • 2017
  • Ingår i: European journal of mineralogy. - 0935-1221. ; 29:5, s. 889-896
  • Tidskriftsartikel (refereegranskat)abstract
    • Oxy-foitite, □(Fe2+Al2)Al6(Si6O18)(BO3)3(OH)3O, is a new mineral of the tourmaline supergroup. It occurs in high-grade migmatitic gneisses of pelitic composition at the Cooma metamorphic Complex (New South Wales, Australia), in association with muscovite, K-feldspar and quartz. Crystals are black with a vitreous luster, sub-conchoidal fracture and gray streak. Oxy-foitite has a Mohs hardness of ∼7, and has a calculated density of 3.143 g/cm3. In plane-polarized light, oxy-foitite is pleochroic (O= dark brown and E = pale brown), uniaxial negative. Oxy-foitite belongs to the trigonal crystal system, space group R3m, a = 15.9387(3) Å, c = 7.1507(1)Å and V = 1573.20(6)Å3,Z = 3. The crystal structure of oxy-foitite was refined to R1 = 1.48% using 3247 unique reflections from single-crystal X-ray diffraction using MoKα radiation. Crystal-chemical analysis resulted in the empirical structural formula: X(□0.53Na0.45Ca0.01K0.01)Σ1.00Y(Al1.53Fe2+1.16Mg0.22Mn2+0.05Zn0.01Ti4+0.03)Σ3.00Z(Al5.47Fe3+0.14Mg0.39)Σ6.00[(Si5.89Al0.11)Σ6.00O18](BO3)3V(OH)3W[O0.57F0.04(OH)0.39]Σ1.00. Oxy-foitite belongs to the X-site vacant group of the tourmaline-supergroup minerals, and shows chemical relationships with foitite through the substitution YAl3++WO2-→YFe2++W(OH)1–.
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  • Holtstam, Dan, et al. (författare)
  • Delhuyarite-(Ce) – Ce4Mg(Fe3+2W)□(Si2O7)2O6(OH)2 – a new mineral of the chevkinite group, from the Nya Bastnäs Fe–Cu–REE deposit, Sweden
  • 2017
  • Ingår i: European journal of mineralogy. - 0935-1221. ; 29:5, s. 897-905
  • Tidskriftsartikel (refereegranskat)abstract
    • Delhuyarite-(Ce) is a new mineral (IMA no. 2016-091) with ideal formula Ce4Mg(Fe3+2W)□(Si2O7)2O6(OH)2. It is named after Juan and Fausto de Elhuyar (Delhuyar), chemists and metallurgists, who in 1783 isolated tungsten metal for the first time.  Associated minerals in the only known sample, from the Nya Bastnäs Fe–Cu–REE deposit (Västmanland, Sweden), include cerite-(Ce), tremolite‒actinolite, percleveite-(Ce), bastnäsite-(Ce), ferriallanite-(Ce), törnebohmite-(Ce), magnetite, chalcopyrite, quartz and scheelite. Delhuyarite-(Ce), which forms subhedral crystals up to 0.3mm long, is brown–black with a dark brown streak and translucent with an adamantine lustre. It is pleochroic in black to rust red and optically biaxial (-). Calculated density and mean refractive index are 5.20 g·cm-3 and 1.94, respectively. Chemical analyses (electron microprobe) gave (in wt%) La2O3 14.58, Ce2O3 23.29, Pr2O3 1.89, Nd2O3 6.13, Sm2O3 0.74, Gd2O3 0.37, Dy2O3 0.03, Er2O3 0.04, Yb2O3 0.12, Y2O3 0.22, CaO 0.76, Fe2O3 12.86, MgO 2.43, Al2O3 0.73, SiO2 18.16, TiO2 0.09, WO3 15.53, H2Ocalc 1.33, F 0.05, Cl 0.03, O=(F, Cl) 0.03, sum 99.35, corresponding to an empirical formula: (Ce1.89La1.19Nd0.48Pr0.15Sm0.06Gd0.03Y0.03Ca0.18)Σ4.01(Fe3+2.14W0.89Mg0.80Al0.19Ti0.02)Σ4.04Si4.01O20(OH1.96F0.04)Σ2, based on 22 O atoms per formula unit (apfu). The presence of H2O is confirmed by IR-spectroscopy, from a strong absorption band at 3495 cm-1. Delhuyarite-(Ce) is monoclinic, space group C2/m, with unit-cell parameters a =13.6020(6)Å, b = 5.7445(3)Å, c = 10.9996(5)Å, β = 100.721(4)°, V = 844.47 (6)Å3 and Z = 2 (data for natural crystal). The crystal structure was refined to an R1 index of 3.9% (natural crystal) and 1.8% (annealed). Delhuyarite-(Ce) has the same structural topology as chevkinite subgroup minerals, e.g. chevkinite-(Ce). It is the only mineral of the group with a significant content of W6+ = 0.89 apfu. In delhuyarite-(Ce), Mg is dominant at the M1 site as in polyakovite-(Ce); the composition of the M2, M3 and M4 sites is [(Fe3+2W)□], with M2 being 50% vacant.
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14.
  • Holtstam, Dan, et al. (författare)
  • Ulfanderssonite-(Ce), a new Cl-bearing REE silicate mineral species from the Malmkärra mine, Norberg, Sweden
  • 2017
  • Ingår i: European journal of mineralogy. - 0935-1221. ; 29:6, s. 1015-1026
  • Tidskriftsartikel (refereegranskat)abstract
    • Ulfanderssonite-(Ce) is a new mineral (IMA 2016-107) from the long-abandoned Malmkärra iron mine, one of the Bastnäs-type Fe-rare earth element (REE) deposits in the Bergslagen ore region, central Sweden. It is named for Ulf B. Andersson, a Swedish geologist and petrologist. In the type specimen, the mineral occurs with västmanlandite-(Ce), bastnäsite-(Ce), phlogopite, talc, magnetite, pyrite, fluorbritholite-(Ce) and scheelite. Ulfanderssonite-(Ce) forms pinkish, translucent subhedral grains, 100-300 mu m, in aggregates up to 2 mm. Fracture is uneven, and there is an indistinct cleavage parallel (001). Mohs' hardness is 5-6, D-calc = 4.97 g cm(-3). Optically, ulfanderssonite-(Ce) is nonpleochroic, biaxial negative, with 2V(meas) = 55 degrees and n(calc) = 1.82. The ideal composition is Ce15CaMg2(SiO4)(10)(SiO3OH)(OH,F)(5)Cl-3. Electron microprobe and LA-ICP-MS chemical analyses yielded (in wt%) La2O3 11.87, Ce2O3 30.98, Pr2O3 3.99, Nd2O3 17.14, Sm2O3 2.81, Eu2O3 0.18, Gd2O3 1.15, Dy2O3 0.30, Tb2O3 0.10, Y2O3 1.11, CaO 2.26, FeO 0.02, MgO 1.97, P2O5 0.08, SiO2 19.13, H2Ocalc 1.07, F 1.09, Cl 2.89, O=(F, Cl) -1.10, sum 97.04. The five strongest powder X-ray diffraction lines are [I(%) d(obs) (angstrom) (hkl)]: 100 2.948 (- 421), 47 2.923 (204), 32 2.660 (- 225), 26 3.524 (40-1), 25 1.7601 (6-23). Ulfanderssonite-(Ce) is monoclinic, Cm, with a = 14.1403(8), b = 10.7430(7), c = 15.498(1) angstrom, b = 106.615(6)degrees and V = 2256.0 (2) angstrom 3 for Z = 2. The crystal structure has been solved by direct methods and refined to R-1 = 2.97% for 5280 observed reflections. It consists of a regular alternation of two layers, designated A and B, along the c-axis: A (ca. 9 angstrom thickness), with composition [(Ce8Ca) MgSi7O22(OH, F) 4](8+), and B (ca. 6.5 angstrom), with composition [Ce7MgSi4O21(OH, F)(2)Cl-3](8); the A layer is topologically and chemically closely related to cerite-(Ce). A FTIR spectrum shows strong absorption in the region 2850-3650 cm(-1), related to the presence of OH stretching bands. Ulfanderssonite-(Ce) is interpreted as a primary mineral at the deposit, along with the more common fluorbritholite-(Ce), formed by a magmatic-hydrothermal fluid with REE, Si, F and Cl ion complexes reacting with dolomite marble. The presence of ulfanderssonite-(Ce) is direct evidence of a Cl-rich mineral-forming aqueous solution, normally not reflected in the composition of skarn minerals in Bastnäs-type deposits.
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  • Nilsson, E.J. Charlotta, et al. (författare)
  • A nuclear geochemical analysis system for boron quantification using a focused ion beam
  • 2017
  • Ingår i: Journal of Radioanalytical and Nuclear Chemistry. - Kluwer. - 0236-5731. ; 311:1, s. 355-364
  • Tidskriftsartikel (refereegranskat)abstract
    • Ion beam analysis has for decades been used as a tool for geochemical analysis of trace elements using both X-rays (particle induced X-ray emission) and nuclear reaction analysis. With the geoanalytical setup at the Lund Ion Beam Analysis Facility, the boron content in geological samples with a spatial resolution of 1 µm is determined through nuclear reaction analysis. In the newly upgraded setup, a single detector has been replaced by a double sided silicon strip detector with 2048 segments. After optimization, boron content in geological samples as low as 1 µg g−1 can be measured.
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  • Biagioni, Cristian, et al. (författare)
  • The crystal structure of svabite, Ca5(AsO4)3F, an arsenate member of the apatite supergroup
  • 2016
  • Ingår i: American Mineralogist. - 0003-004X. ; 101, s. 1750-1755
  • 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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24.
  • Bosi, Ferdinando, et al. (författare)
  • Crystal chemistry of spinels in the system MgAl2O4-MgV2O4-Mg2VO4
  • 2016
  • Ingår i: American Mineralogist. - 0003-004X. ; 101, s. 580-586
  • 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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  • Bosi, Ferdinando, et al. (författare)
  • Thermally induced cation redistribution in Fe‑bearing oxy‑dravite and potential geothermometric implications
  • 2016
  • Ingår i: Contributions to Mineralogy and Petrology. - 0010-7999. ; 171:5, s. 1-14
  • Tidskriftsartikel (refereegranskat)abstract
    • Iron-bearing oxy-dravite was thermally treated in air and hydrogen atmosphere at 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 intersite geothermometry based on tourmaline. Overall, the experimental data (structural refinement, Mössbauer, infrared and optical absorption spectroscopy) show that heating Fe-bearing tourmalines results in disordering of Fe over Y and Z balanced by ordering of Mg at Y, whereas Al does not change appreciably. The Fe disorder depends on temperature, but less on redox conditions. The degree of Fe3+–Fe2+ reduction is limited despite strongly reducing conditions, indicating that the fO2 conditions do not exclusively control the Fe oxidation state at the present experimental conditions. Untreated and treated samples have similar short- and long-range crystal structures, which are explained by stable Al-extended clusters around the O1 and O3 sites. In contrast to the stable Al clusters that preclude any temperature-dependent Mg–Al order– disorder, there occurs Mg diffusion linked to temperaturedependent exchange with Fe. Ferric iron mainly resides around O2− at O1 rather than (OH)−, but its intersite disorder induced by thermal treatment indicates that Fe redistribution is the driving force for Mg–Fe exchange and that its diffusion rates are significant at these temperatures. With increasing temperature, Fe progressively disorders over Y and Z, whereas Mg orders at Y according to the order–disorder reaction: YFe + ZMg → ZFe + YMg. The presented findings are important for interpretation of the post-crystallization history of both tourmaline and tourmaline host rocks and imply that successful tourmaline geothermometers may be developed by thermal calibration of the Mg– Fe order–disorder reaction, whereas any thermometers based on Mg–Al disorder will be insensitive and involve large uncertainties.
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