Crystal-chemistry of sulfates from the Apuan Alps (Tuscany, Italy). VI. Tl-bearing alum-(K) and voltaite from the Fornovolasco mining complex

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Crystal-chemistry of sulfates from the Apuan Alps (Tuscany, Italy). VI. Tl-bearing alum-(K) and voltaite from the Fornovolasco mining complex. / Biagioni, Cristian; Mauro, Daniela; Pasero, Marco et al.
In: American mineralogist, The, Vol. 105, No. 7, 28.07.2020, p. 1088-1098.

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Biagioni C, Mauro D, Pasero M, Bonaccorsi E, Lepore GO, Zaccarini F et al. Crystal-chemistry of sulfates from the Apuan Alps (Tuscany, Italy). VI. Tl-bearing alum-(K) and voltaite from the Fornovolasco mining complex. American mineralogist, The. 2020 Jul 28;105(7):1088-1098. doi: 10.2138/am-2020-7320

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@article{d48b6726712e42a19171b81b68305251,
title = "Crystal-chemistry of sulfates from the Apuan Alps (Tuscany, Italy). VI. Tl-bearing alum-(K) and voltaite from the Fornovolasco mining complex",
abstract = "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), M{\"o}ssbauer, 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 NH4+ $\text{NH}_{4}^{+}$ was detected through FTIR spectroscopy. Its unit-cell parameter is a = 12.2030(2) {\AA}, V = 1817.19(9) {\AA}3, space group Pa3¯. $Pa\bar{3}.$Its crystal structure has been refined down to R1 = 0.0351 for 648 reflections with F o > 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) {\AA}. Voltaite occurs as dark green cubic crystals, up to 1 mm in size. Voltaite is chemically zoned, with distinct domains having chemical formula (K1.94Tl0.28)σ2.22(Fe2+3.57Mg0.94Mn0.55)σ5.06Fe3+3.06Al0.98S11.92O4818H2O and (K2.04Tl0.32)σ2.36(Fe2+3.83Mg0.91Mn0.29)σ5.03Fe3+3.05Al0.97S11.92O48 18H2O, respectively. Infrared spectroscopy confirmed the occurrence of minor NH4+ also in voltaite. Its unit-cell parameter is a = 27.2635 {\AA}, V = 20265(4) {\AA}3, space group Fd3c. 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) {\AA}. 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.",
keywords = "Alum-(K), Apuan alps, Crystal structure, Fornovolasco, Italy, thallium, Tuscany, Voltaite, Xas",
author = "Cristian Biagioni and Daniela Mauro and Marco Pasero and Elena Bonaccorsi and Lepore, {Giovanni Orazio} and Federica Zaccarini and Henrik Skogby",
note = "Publisher Copyright: {\textcopyright} 2020 Walter de Gruyter GmbH, Berlin/Boston 2020",
year = "2020",
month = jul,
day = "28",
doi = "10.2138/am-2020-7320",
language = "English",
volume = "105",
pages = "1088--1098",
journal = "American mineralogist, The",
issn = "0003-004X",
publisher = "Mineralogical Society of America",
number = "7",

}

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TY - JOUR

T1 - Crystal-chemistry of sulfates from the Apuan Alps (Tuscany, Italy). VI. Tl-bearing alum-(K) and voltaite from the Fornovolasco mining complex

AU - Biagioni, Cristian

AU - Mauro, Daniela

AU - Pasero, Marco

AU - Bonaccorsi, Elena

AU - Lepore, Giovanni Orazio

AU - Zaccarini, Federica

AU - Skogby, Henrik

N1 - Publisher Copyright: © 2020 Walter de Gruyter GmbH, Berlin/Boston 2020

PY - 2020/7/28

Y1 - 2020/7/28

N2 - 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 NH4+ $\text{NH}_{4}^{+}$ was detected through FTIR spectroscopy. Its unit-cell parameter is a = 12.2030(2) Å, V = 1817.19(9) Å3, space group Pa3¯. $Pa\bar{3}.$Its crystal structure has been refined down to R1 = 0.0351 for 648 reflections with F o > 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 (K1.94Tl0.28)σ2.22(Fe2+3.57Mg0.94Mn0.55)σ5.06Fe3+3.06Al0.98S11.92O4818H2O and (K2.04Tl0.32)σ2.36(Fe2+3.83Mg0.91Mn0.29)σ5.03Fe3+3.05Al0.97S11.92O48 18H2O, respectively. Infrared spectroscopy confirmed the occurrence of minor NH4+ also in voltaite. Its unit-cell parameter is a = 27.2635 Å, V = 20265(4) Å3, space group Fd3c. 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.

AB - 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 NH4+ $\text{NH}_{4}^{+}$ was detected through FTIR spectroscopy. Its unit-cell parameter is a = 12.2030(2) Å, V = 1817.19(9) Å3, space group Pa3¯. $Pa\bar{3}.$Its crystal structure has been refined down to R1 = 0.0351 for 648 reflections with F o > 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 (K1.94Tl0.28)σ2.22(Fe2+3.57Mg0.94Mn0.55)σ5.06Fe3+3.06Al0.98S11.92O4818H2O and (K2.04Tl0.32)σ2.36(Fe2+3.83Mg0.91Mn0.29)σ5.03Fe3+3.05Al0.97S11.92O48 18H2O, respectively. Infrared spectroscopy confirmed the occurrence of minor NH4+ also in voltaite. Its unit-cell parameter is a = 27.2635 Å, V = 20265(4) Å3, space group Fd3c. 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.

KW - Alum-(K)

KW - Apuan alps

KW - Crystal structure

KW - Fornovolasco

KW - Italy

KW - thallium

KW - Tuscany

KW - Voltaite

KW - Xas

UR - http://www.scopus.com/inward/record.url?scp=85089885300&partnerID=8YFLogxK

U2 - 10.2138/am-2020-7320

DO - 10.2138/am-2020-7320

M3 - Article

VL - 105

SP - 1088

EP - 1098

JO - American mineralogist, The

JF - American mineralogist, The

SN - 0003-004X

IS - 7

ER -