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The new mineral batoniite, [Al 8 (OH) 14 (H 2 O) 18 ](SO 4)5 ⋅ 5H 2 O, was discovered in the Cetine di Cotorniano Mine, Chiusdino, Siena, Tuscany, Italy. It occurs as hemispherical aggregates composed of brittle tabular crystals, up to 1 mm in size, white to colorless in color, with a white streak and a vitreous to greasy luster. Batoniite is biaxial negative, with α= 1.4833(6), β= 1.4948(6), γ= 1.5019(5) (589 nm), and 2 V(meas.)= 71(1) ∘. Electron microprobe analysis, affected by the dehydration of batoniite under the chamber vacuum, gave (in wt %) the following: Al 2 O 3 33.48, Fe 2 O 3 0.05, SO 3 33.00, and H 2 O calc 44.41, total 110.94. It corresponds to the chemical formula (Al 7.98 Fe 0.013+)Σ7.99 (SO 4)5.01 (OH) 13.95 (H 2 O) 18 ⋅ 5H 2 O. Batoniite is triclinic, belonging to space group P1‾ , with a= 9.1757(6), b= 12.0886(9), c= 20.9218(15) Å, α= 82.901(3), β= 87.334(3), γ= 86.999(2) ∘ , V= 2297.8(3) Å 3 , and Z= 2. The crystal structure was refined to R1= 0.0916 for 8118 unique reflections with Fo>4σ(Fo) and 811 refined parameters and 60 restraints. Batoniite is characterized by isolated [Al 8 (OH) 14 (H 2 O) 18 ] 10+ polyoxocations, H-bonded to five interstitial (SO 4) 2- and five H 2 O groups. In type material, it is associated with gypsum and a poorly crystallized Al–Fe sulfate. The crystallization of batoniite is probably due to the action of H 2 SO 4 on Al-bearing rocks of Paleozoic age cropping out in the Garibaldi Tunnel, the lowest mining level of the Cetine di Cotorniano Mine. [ABSTRACT FROM AUTHOR]

The new tourmaline supergroup mineral dutrowite, Na(Fe 2.52+ Ti 0.5)Al 6 (Si 6 O 18)(BO 3) 3 (OH) 3 O, has been discovered in an outcrop of a Permian metarhyolite near the hamlet of Fornovolasco, Apuan Alps, Tuscany, Italy. It occurs as chemically homogeneous domains, up to 0.5 mm, brown in colour, with a light-brown streak and a vitreous lustre, within anhedral to subhedral prismatic crystals, up to 1 mm in size, closely associated with Fe-rich oxy-dravite. Dutrowite is trigonal, space group R 3 m , with a=15.9864(8) , c=7.2187(4) Å, V=1597.68(18) Å 3 , and Z=3. The crystal structure was refined to R1=0.0257 for 1095 unique reflections with Fo>4σ (Fo) and 94 refined parameters. Electron microprobe analysis, coupled with Mössbauer spectroscopy, resulted in the empirical structural formula X (Na 0.81 Ca 0.20 K 0.01) Σ1.02 Y (Fe 1.252+ Mg 0.76 Ti 0.56 Al 0.42) Σ3.00 Z (Al 4.71 Fe 0.273+ V 0.023+ Mg 0.82 Fe 0.182+) Σ6.00 T [(Si 5.82 Al 0.18) Σ6.00 O 18 ] (BO 3)3O(3) (OH) 3O(1) [O 0.59 (OH) 0.41 ] Σ1.00 , which was recast in the empirical ordered formula, required for classification purposes: X (Na 0.81 Ca 0.20 K 0.01) Σ1.02 Y (Fe 1.432+ Mg 1.00 Ti 0.56) Σ3.00 Z (Al 5.13 Fe 0.273+ V 0.023+ Mg 0.58) Σ6.00 T [(Si 5.82 Al 0.18) Σ6.00 O 18 ] (BO 3) 3V (OH) 3 W [O 0.59 (OH) 0.41 ] Σ1.00. Dutrowite is an oxy-species belonging to the alkali group of the tourmaline supergroup. Titanium is hosted in octahedral coordination, and its incorporation is probably due to the substitution 2Al 3+ = Ti 4+ + (Fe,Mg) 2+. Its occurrence seems to be related to late-stage high-T/low-P replacement of "biotite" during the late-magmatic/hydrothermal evolution of the Permian metarhyolite. [ABSTRACT FROM AUTHOR]

Although everything seemed clear about the Ag-Sb-S compounds belonging to one of the more deeply studied experimental systems, nature allowed us to discover a new polymorph of Ag3SbS3, which could represent a compound for assessing new technological potentialities. The new mineral species pyradoketosite, Ag3SbS3 (IMA 2019-132), was discovered in the pyrite + baryte + iron oxide ore deposit of the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. It occurs as brittle orange acicular crystals, up to 200 μm in length and 25 μm in thickness, with adamantine luster. Under reflected light, pyradoketosite is slightly bluish-gray, with abundant orange internal reflections. Bireflectance is weak, and anisotropism was not observed, being masked by abundant internal reflections. Minimum and maximum reflectance data for the wavelengths recommended by the Commission on Ore Mineralogy [Rmin/Rmax (%) (λ, nm)] are 32.8/32.9 (470), 30.2/30.7 (546), 29.0/29.6 (589), and 27.5/28.4 (650). Electron microprobe analysis gave (mean of 6 spot analyses, in wt%): Ag 59.81, Sb 22.63, S 17.78, total 100.22. On the basis of (Ag+Sb) = 4 atoms per formula unit, the empirical formula of pyradoketosite is Ag2.996(11)Sb1.004(11)S2.996(15). Pyradoketosite is monoclinic, space group P21/n, with a = 13.7510(15), b = 6.9350(6), c = 19.555(2) Å, β = 94.807(4)°, V = 1858.3(3) Å3, Z = 12. The crystal structure was solved and refined to R1 = 0.063 on the basis of 2682 unique reflections with Fo> 4σ(Fo) and 191 refined parameters. The structure of pyradoketosite can be described as formed by the alternation of {101} layers: an Sb-rich layer, Sb3AgS3, and two distinct Ag8S6 layers. This layered organization allows identifying structural relationships with the wittichenite-skinnerite pair. Pyradoketosite is associated with pyrargyrite, tetrahedrite-(Hg), valentinite, and probable pyrostilpnite in baryte + dolomite + quartz veins embedded in metadolostone. Its name derives from the old Greek words "πυρ" (fire) and "άδόκητος" (unforeseen), because of the unexpected occurrence of this third polymorph of the compound Ag3SbS3. [ABSTRACT FROM AUTHOR]

A crystal-chemical study of historical specimens as well as new ones belonging to the jordanite-geocronite series from the Pollone baryte + pyrite ± (Pb-Zn-Ag) ore deposit (Valdicastello Carducci, Apuan Alps, Tuscany, Italy) has been performed. These crystals were collected in quartz extension veins embedded in three different occurrences: (i) baryte + pyrite orebodies; (ii) schist layers interbedded between baryte + pyrite orebodies; and (iii) schists at the contact with pyrite-poor baryte orebodies. Electron-microprobe data indicated the occurrence of three distinct groups of compositions within the sample suite. These correspond to As-bearing geocronite, Sb-rich jordanite, and Sb-bearing jordanite, with mean compositions Pb14Sb3.8As2.2S23, Pb14Sb2.9As3.1S23, and Pb14Sb2.6As3.4S23, respectively. Crystals representative of these different compositions have been investigated through single-crystal X-Ray diffraction studies and their crystal structures have been solved to R1 = 0.078, 0.069, and 0.033, respectively. The unit-cell volume decreases passing through As-bearing geocronite (V = 2149.5(3) ų) to Sb-bearing jordanite (V = 2132.3(3) ų). The As-to-Sb substitution takes place preferentially at the Sb4 site; through the increasing of the Sb content, Sb can substitute As also at the As6 site. According to the structural study of the ore deposit, formation of jordanite-geocronite is subordinated to a late Alpine deformative D2 stage, which permitted in situ remobilization of preexisting sulfide ore in small quartz extension veins. Such a local recrystallization would explain the variability of the As/(As + Sb) ratio of the members of the jordanite series, reflecting the heterogeneity of the orebody. [ABSTRACT FROM AUTHOR]

SEM-EDX quantitative analyses were performed on 91 samples of vessel glass originating from a number of sites throughout Tuscany. A comparison with Venetian glass data is made in order to evaluate differences in glassmaking materials. The compositions of the samples provide clues about the different raw materials used in relation to recipes that changed slightly during the period covering the late Middle Ages to early Renaissance. Two kinds of ash used as a fluxing agent were identified, one of which is of east Mediterranean origin while the other is likely to be Spanish. Two types of silica sources were also found. One of these was recognized as being quartziferous river pebbles, while the other is proposed to be local sand. [ABSTRACT FROM AUTHOR]

The new mineral species magnanelliite, K3Fe3+2(SO4)4(OH)(H2O)2, was discovered in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. It occurs as steeply terminated prisms, up to 0.5 mm in length, yellow to orange-yellow in color, with a vitreous luster. Streak is pale yellow, Mohs hardness is ca. 3, and cleavage is good on {010}, fair on {100}. The measured density is 2.82(3) g/cm3. Magnanelliite is optically biaxial (+), with α = 1.628(2), β = 1.637(2), γ = 1.665(2) (white light), 2Vmeas = 60(2)°, and 2Vcalc = 59.9°. It exhibits a strong dispersion, r > v. The optical orientation is Y = b, X ^ c ~ 25° in the obtuse angle β. It is pleochroic, with X = orange yellow, Y and Z = yellow. Magnanelliite is associated with alum-(K), giacovazzoite, gypsum, jarosite, krausite, melanterite, and scordariite. Electron microprobe analyses give (wt.%): SO3 47.82, TiO2 0.05, Al2O3 0.40, Fe2O3 25.21, MgO 0.07, Na2O 0.20, K2O 21.35, H2Ocalc 6.85, total 101.95. On the basis of 19 anions per formula unit, assuming the occurrence of one (OH)− and two H2O groups, the empirical chemical formula of magnanelliite is (K2.98Na0.04)Σ3.02(Fe3+2.08Al0.05Mg0.01)Σ2.14S3.93O16(OH)(H2O)2. The ideal end-member formula can be written as K3Fe3+2(SO4)4(OH)(H2O)2. Magnanelliite is monoclinic, space group C2/c, with a = 7.5491(3), b = 16.8652(6), c = 12.1574(4) Å, β = 94.064(1)°, V = 1543.95(10) Å3, Z = 4. Strongest diffraction lines of the observed X-ray powder pattern are [d(in Å), estimated visual intensity, hkl]: 6.9, medium, 021 and 110; 4.91, medium-weak, 022; 3.612, medium-weak, 1 ¯ 32, 023, and 1 ¯ 13; 3.085, strong, 202, 150, and 1 ¯ 33; 3.006, medium, 004, 1 ¯ 51, and 151; 2.704, medium, 152 and 2 ¯ 23; 2.597, medium-weak, 2 ¯ 42; 2.410, medium-weak, 153. The crystal structure of magnanelliite has been refined using X-ray single-crystal data to a final R1 = 0.025, on the basis of 2411 reflections with Fo > 4σ(Fo) and 144 refined parameters. The crystal structure is isotypic with that of alcaparrosaite, K3Ti4+Fe3+(SO)4O(H2O)2. [ABSTRACT FROM AUTHOR]

The new mineral species scordariite, K8(Fe3+0.67□0.33)[Fe3+3O(SO4)6(H2O)3]2(H2O)11, was discovered in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. It occurs as pseudo-hexagonal tabular crystals, yellowish to brownish in color, up to 0.5 mm in size. Cleavage is perfect on {0001}. It is associated with giacovazzoite, krausite, gypsum, jarosite, alum-(K), and magnanelliite. Electron microprobe analyses give (wt %): SO3 47.31, Al2O3 0.66, Fe2O3 24.68, FeO 0.69, Na2O 0.52, K2O 17.36, H2Ocalc 15.06, total 106.28. The partitioning of Fe between Fe2+ and Fe3+ was based on Mössbauer spectroscopy. On the basis of 67 O atoms per formula unit, the empirical chemical formula is (K7.50Na0.34)Σ7.84(Fe3+6.29Al0.26Fe2+0.20)Σ6.75S12.02O50·17H2O. The ideal end-member formula can be written as K8(Fe3+0.67□0.33)[Fe3+3O(SO4)6(H2O)3]2(H2O)11. Scordariite is trigonal, space group R-3, with (hexagonal setting) a = 9.7583(12), c = 53.687(7) Å, V = 4427.4(12) Å3, Z = 3. The main diffraction lines of the observed X-ray powder pattern are [d(in Å), estimated visual intensity]: 8.3, strong; 6.6, medium; 3.777, medium; 3.299, medium; 3.189, medium; 2.884, strong. The crystal structure of scordariite has been refined using X-ray single-crystal data to a final R1 = 0.057 on the basis of 1980 reflections with Fo > 4σ(Fo) and 165 refined parameters. It can be described as a layered structure formed by three kinds of layers. As with other metavoltine-related minerals, scordariite is characterized by the occurrence of the [Fe3+3O(SO4)6(H2O)3]5− heteropolyhedral cluster. [ABSTRACT FROM AUTHOR]

The new mineral species tiberiobardiite, ideally Cu9Al(SiO3OH)2(OH)12(H2O)6(SO4)1.5·10H2O, has been discovered in the Cretaio Cu prospect, Massa Marittima, Grosseto, Tuscany, Italy, as very rare, light green, vitreous, tabular {0001}, pseudo-hexagonal crystals, up to 200 μm in size and 5 μm in thickness, associated with brochantite. Electron microprobe analysis gave (in wt %, average of 5 spot analyses): SO3 10.37, P2O5 3.41, As2O5 0.05, SiO2 8.13, Al2O3 5.54, Fe2O3 0.74, CuO 62.05, and ZnO 0.03, for a total of 90.32. Based on an idealized O content of 42 atoms per formula unit, assuming the presence of 16 H2O groups and 13.5 cations (without H), the empirical formula of tiberiobardiite is (Cu8.69Al0.21Fe0.10)Σ9.00Al1.00(Si1.51P0.54)Σ2.05S1.44O12.53(OH)13.47·16H2O. The main diffraction lines, corresponding to multiple hkl indices, are [d in Å (relative visual intensity)]: 9.4 (s), 4.67 (s), 2.576 (m), 2.330 (m), and 2.041 (mw). The crystal structure study revealed tiberiobardiite to be trigonal, space group R 3 ¯ , with unit-cell parameters a = 10.6860(4), c = 28.3239(10) Å, V = 2801.0(2) Å3, and Z = 3. The crystal structure was refined to a final R1 = 0.060 for 1747 reflections with Fo > 4σ (Fo) and 99 refined parameters. Tiberiobardiite is the Si-analogue of chalcophyllite, with Si4+ replacing As5+ through the coupled substitution As5+ + O2− = Si4+ + (OH)−. The name tiberiobardiite honors Tiberio Bardi (b. 1960) for his contribution to the study of the mineralogy of Tuscany. [ABSTRACT FROM AUTHOR]