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(searched for: doi:10.1007/s00269-019-01076-4)
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Published: 15 February 2021
by MDPI
Abstract:
A suite of sulfate minerals from the Monte Arsiccio mine (Apuan Alps, Northern Tuscany, Italy), previously identified by using both X-ray diffraction and micro-Raman spectroscopy, was studied through inductively coupled plasma mass spectrometry (ICP-MS), in order to determine their trace-element content. Several elements (Tl, Rb, As, Sb, Co, Ni, Cu, Zn, and Cr) were found above the detection limits. Among them, some are important from an environmental perspective and may reach relatively high concentrations (e.g., Tl = 1370–2988 μg/g; As = 505–1680 μg/g). Thus, these sulfates may act as transient sinks for some of these potentially toxic elements, as well as for sulfate ions and acidity. Indeed, dissolution experiments revealed the ability of these secondary minerals to produce a significant pH decrease of the solutions, as well as the release of Fe, Al, and K as major ions. This work discusses the relation between the budget of trace elements and the crystal chemistry of sulfate minerals and provides new insights about the environmental role played by the sulfate dissolution in controlling the quality of water in acid mine drainage systems.
Published: 5 December 2020
by MDPI
Abstract:
The occurrence of sulfate minerals associated with the pyrite ores of the southern Apuan Alps has been known since the 19th century but modern mineralogical studies started only in the last decade. Sulfate assemblages were identified in all the pyrite ore deposits from the studied area but the more impressive associations were discovered in the Fornovolasco and Monte Arsiccio mines. Their study allowed to improve the knowledge of the sulfate crystal-chemistry and to achieve a better understanding of the acid mine drainage (AMD) systems associated with pyrite oxidation. More than 20 different mineral species were identified and, among them, four sulfates (volaschioite, giacovazzoite, magnanelliite, and scordariite) have their type localities in the pyrite ore deposits of the Apuan Alps. A review of the mineralogical results of a ten-year-long study is given here.
Maria Lacalamita, Emanuela Schingaro, Ernesto Mesto, Federica Zaccarini, Cristian Biagioni
Published: 19 November 2020
Physics and Chemistry of Minerals, Volume 47; https://doi.org/10.1007/s00269-020-01118-2

Abstract:
The present work reports the crystal-chemical characterization of micas from the Monte Arsiccio and Buca della Vena mines (Apuan Alps, Italy) through electron microprobe analysis, single-crystal X-ray diffraction, and Raman spectroscopy. The sample from the Monte Arsiccio mine can be classified as an intermediate member of the yangzhumingite-fluorophlogopite series, with average crystal-chemical formula (K0.85Na0.01Ba0.09)Σ=0.95(Mg2.11Fe2+0.23Fe3+0.11Cr3+0.01Al0.20Ti0.040.30)Σ=3.00(Si3.20Al0.80)Σ=4.00O10.00F1.90Cl0.02(OH)0.08. Unit-cell parameters are a ~ 5.30, b ~ 9.18, c ~ 10.14 Å, β ~ 100.12°, V ~ 486.22 Å3, corresponding to the 1M polytype. Structure refinements, performed in C2/m space group, converged to R1 = 3.54 and 4.46% and provided Mg plus Fe occupancy in the range 86–94% for the octahedral M1 and M2 sites. Raman spectroscopy shows very weak bands in the OH stretching region at ~ 3690 and 3580 cm−1. The sample from the Buca della Vena mine has been identified as an (OH)-rich fluorophlogopite, with average crystal-chemical formula (K0.84Na0.02Ca0.01)Σ=0.87(Mg2.12Fe2+0.55Fe3+0.10Al0.180.05)Σ=3.00(Si2.99Al1.01)Σ=4.00O10.00F1.02Cl0.09(OH)0.89. Its unit-cell parameters are a ~ 5.33, b ~ 9.22, c ~ 10.23 Å, β ~ 100.09°, V ~ 494.39 Å3. Structure refinements gave good R1 values (3.27 and 4.37%) and revealed octahedral occupancy of 82–84% Mg and 16–18% Fe. Strong Raman signals at ~ 3702 cm−1 and 3595 cm−1 were observed in the OH stretching region. The findings allow to better understand not only the mineralogy of the Apuan Alps but, more generally, the crystal chemical details of intermediate dioctahedral-trioctahedral mica belonging to the yanzhumingite-fluorophlogopite series.
, Cristian Biagioni, Marco Pasero, Federica Zaccarini
Published: 30 June 2020
Mineralogical Magazine, Volume 84, pp 540-546; https://doi.org/10.1180/mgm.2020.51

Abstract:
Khademite, ideally Al(SO4)F(H2O)5, from the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy, has been characterised through quantitative electron microprobe analysis, micro-Raman spectroscopy and single-crystal X-ray diffraction. Khademite occurs as colourless to whitish tabular crystals, up to 5 mm. Electron microprobe analysis (in wt.%, average of 20 spot analyses) gave: SO3 35.43, Al2O3 21.27, F 6.92, H2Ocalc 39.73, sum 103.35, –O = F 2.92, total 100.43. On the basis of 10 anions per formula unit, assuming the occurrence of 5 H2O groups and 1 (F+OH) atom per formula unit, its chemical formula can be written as Al0.96S1.02O4[F0.84(OH)0.16]Σ1.00⋅5H2O. The Raman spectrum of khademite is characterised by the occurrence of vibrational modes of SO4 groups and by broad and strong bands due to the O–H stretching modes. Khademite is orthorhombic, space group Pcab, with unit-cell parameters a = 11.1713(2), b = 13.0432(3), c = 10.8815(2) Å, V = 1585.54(5) Å3 and Z = 8. The crystal structure refinement converged to R1 = 0.0293 on the basis of 2359 unique reflections with Fo > 4σ(Fo) and 152 refined parameters. The crystal structure of khademite is characterised by the alternation, along b, of two distinct kinds of {010} layers, one formed by [001] rows of isolated Al-centred octahedra, connected to each other through H bonds, and the other showing isolated SO4 groups. Along b, oxygen atoms belonging to SO4 groups act as acceptor of H bonds from H2O groups coordinating Al atoms. The new data improved the description of the H bonds in khademite and led us to discuss about the possible existence of its (OH)-analogue, rostite. In addition, Raman spectroscopic data were collected on the same crystal used for the crystal-chemical characterisation, allowing a comparison with previous results.
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