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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]

The plagionite homologous series contains four well-defined members with the general formula Pb1+2NSb8S13+2N: fülöppite (N = 1), plagionite (N D 2), heteromorphite (N = 3), and semseyite (N = 4). The crystal structure of several natural and synthetic samples of fülöppite, plagionite, and semseyite have been refined through single-crystal X-ray diffraction, confirming the systematic Pb-versus-Sb crossed substitution observed previously in semseyite and fülöppite. This crossed substitution takes place mainly in two adjacent cation sites in the middle of the constitutive SnS-type layer. The substitution coefficient x appears variable, even for a given species, with the highest values observed in synthetic fülöppite samples. The developed structural formula of the plagionite homologues can be given as Pb2N-1(Pb1-xSbx)2(Sc1-xPbx)2Sb6S13+2 In the studied samples, x varies between -0.10 and 0.40. In the ribbons within the SnS-type layer, (Pb=Sb) mixing can be considered the result of the combination, in a variable ratio, of two cation sequences, i.e. (Sb--Sb--Sb)--Pb-Sb-(...), major in plagionite and semseyite, and (Sb-Sb-Sb)-Sb-Pb-(...), major in fülöppite and, probably, in heteromorphite. The published crystal structure of synthetic "Pb-free fülöppite" is revised according to this approach. It would correspond to a Na derivative, with a proposed structural formula of (Na0:5Sb0:5/(Na0:2Sb0:8/2(Na0:3Sb0:7/2Sb6S15, ideally Na1:5Sb9:5S15. In fülöppite, increasing x induces a flattening of the unit cell along c, with a slight volume decrease. Such a general Pb-versus-Sb crossed substitution would attenuate steric distortions in the middle of the SnS-type layer of the plagionite homologous series. Crystallization kinetics seem the main physical factor that controls such an isochemical substitution. [ABSTRACT FROM AUTHOR]

Biagioniite, ideally Tl2SbS2, is a new mineral from the Hemlo gold deposit, Marathon, Ontario, Canada. It occurs as very rare anhedral crystals up to 65 μm across associated with aurostibite, stibarsen and native gold in a calcite matrix. Biagioniite is opaque with a metallic lustre and shows a black streak. In reflected light biagioniite is moderately bireflectant and not pleochroic. Under crossed polars it is weakly anisotropic with blueish to light-blue rotation tints. Internal reflections are absent. Reflectance percentages for the four standard wavelengths (Rmin and Rmax) are 35.9 and 37.5 (471.1 nm); 34.7 and 36.2 (548.3 nm); 33.8 and 35.3 (586.6 nm); and 31.5 and 33.7 (652.3 nm), respectively. A mean of four electron microprobe analyses gave: Tl 65.12(31), Ag 3.52(9), Sb 20.22(12), S 10.80(8), total 99.66 wt.%, corresponding, on the basis of a total of 5 atoms, to (Tl1.87Ag0.19)Σ2.06Sb0.97S1.97. Biagioniite is monoclinic, space group Pc, with a = 11.0895(9), b = 14.3124(11), c = 7.9352(6) Å, β = 96.230(8)°, V = 1252.02(17) Å3 and Z = 8. The four strongest powder-diffraction lines [d in Å (I/I0) (hkl)] are: 3.56 (100) (310); 3.37 (75) ($\bar{2}$ 31); 3.79 (60) (012); 3.03 (60) (032). In the crystal structure [R1 = 0.024 for 2655 reflections with I > 2σ(I)], thallium adopts various coordinations extending from quasi-linear to quasi-tetrahedral. Antimony forms Sb–Sb pairs, which lead to the formula [Tl+1]4[Sb2]4+[S2–]4. Biagioniite is isostructural with dervillite, Ag2AsS2. The new mineral has been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA2019–120) and named for Cristian Biagioni, Associate Professor of Mineralogy at the Department of Earth Sciences of the University of Pisa, Italy. [ABSTRACT FROM AUTHOR]