Markwelchite, ideally TlPbSbS3, is a new mineral from the hydrothermal deposit of Jas Roux, Hautes-Alpes, France. It occurs as a black anhedral crystal associated closely with protochabournéite. Microhardness measurements (VHN15) gave a mean value of 197 kg/mm2 corresponding to a Mohs hardness of ~3–4. In plane-polarised incident light, markwelchite is grey in colour. Under crossed polars, it is distinctly anisotropic with greyish white to bluish rotation tints, with bright red internal reflections. Reflectance percentages (Rmin and Rmax) are: 28.5, 31.5 (471.1 nm); 28.3, 30.7 (548.3 nm); 27.9, 30.3 (586.6 nm); and 27.6, 29.8 (652.3 nm). The mean of 5 electron microprobe spot analyses gave Tl 34.67(45), Pb 31.86(25), Sb 15.06(15), As 2.37(5), S 15.35(20), total 99.31 wt.%, corresponding, on the basis of a total of 6 atoms per formula unit and structural results, to Tl1.063Pb0.964(Sb0.775As0.198)Σ0.973S3.000. Single-crystal X-ray diffraction studies revealed that markwelchite is isotypic with richardsollyite, TlPbAsS3. It is monoclinic, space group P21/c, with the following unit-cell parameters: a = 8.9144(3), b = 8.4513(3), c = 8.6511(3) Å, β = 108.723(4)°, V = 617.27(4) Å3 and Z = 4. The five strongest observed powder-diffraction lines [d in Å (Irel)(hkl)] are: 3.88 (100)($\bar{2}$11); 3.78 (90)(210); 3.29 (90)(102); 2.73 (85)($\bar{1}$13); and 2.93 (75)(022). The crystal structure can be described as formed by (100) [Me2(SbS3)]– layers sandwiching the Me1+ cations. The Me1 site has a seven-fold coordination, whereas the Me2 site has an 6+2 coordination corresponding to a distorted, bicapped trigonal prismatic coordination, and the Sb site displays a trigonal pyramidal coordination with three S atoms and Sb at the apex.

The name markwelchite honours Dr Mark D. Welch of the Natural History Museum, London, UK.

The new mineral has been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2024–001). A discussion on the relationships between markwelchite and synthetic TlPbSbS3 is also provided.

Tetrahedrite-(Cu), Cu12Sb4S13, has been approved as a new mineral species (IMA2022–078) from the Bankov magnesite deposit near Košice, Slovak Republic where it occurs as anhedral grains, up to 0.4 mm across, associated with skinnerite, chalcostibite, famatinite, tetrahedrite-(Fe) and zoned aggregates of tennantite-(Cu) to tennantite-(Fe). Tetrahedrite-(Cu) is steel-grey, with a metallic lustre. Mohs hardness is ca. 3½–4 and calculated density is 5.029 g.cm–3. In reflected light, tetrahedrite-(Cu) is isotropic and grey with a bluish shade. Reflectance data for the four COM wavelengths in air are [λ (nm): R (%)]: 470: 31.1; 546: 30.1; 589: 29.9; and 650: 28.1. The empirical formula, based on electron-microprobe data (mean of 17 spot analyses), is Cu11.42Zn0.26Fe0.19(Sb4.06As0.08)Σ4.14S12.99. The ideal formula is Cu6(Cu4Cu2)Sb4S13, which requires (in wt.%) Cu 45.76, Sb 29.23 and S 25.01, total 100.00. Tetrahedrite-(Cu) is cubic, I$\bar{4}$3m, with unit-cell parameters a = 10.3296(15) Å, V = 1102.2(5) Å3 and Z = 2. Its crystal structure was refined by single-crystal X-ray diffraction data to a final R1 = 0.0347 on the basis of 261 unique reflections with Fo > 4σ(Fo) and 22 refined parameters. Tetrahedrite-(Cu) is isotypic with other tetrahedrite-group minerals. Previous findings of tetrahedrite-(Cu) are reported and some nomenclature issues, related to the Fe and Cu oxidation states, are discussed. At the Bankov deposit, tetrahedrite-(Cu) is related to hydrothermal, most probably Alpine, solutions strongly enriched in Cu, Sb and S.

Watanabeite from the Pefka epithermal deposit, northeastern Greece, was examined using single-crystal X-ray diffraction and electron microprobe analysis. The empirical formula of watanabeite is Cu3.93Fe0.10Ag0.01Pb0.23As1.55Sb0.19S4.99. This mineral is orthorhombic, space group Amm2, with unit-cell parameters a = 10.9601(5), b = 14.6498(8), c = 10.3001(5) Å, V = 1653.82(14) Å3 and Z = 8. The crystal structure was solved and refined to R1 = 0.0471 for 2108 unique reflections with Fo > 4σ(Fo) and 123 refined parameters. The crystal structure of watanabeite can be described as a three-dimensional framework of Cu-centred tetrahedra; cavities of the tetrahedral scaffolding host Cu6S and As2(Pb,Sb,As)2S7 clusters. On the basis of structural data, the formula of watanabeite could be written as [III]Cu3[IV]Cu5As3(Pb,Sb,As)S10 (Z = 4), considering the three independent three-fold Cu sites and the three independent tetrahedrally coordinated Cu sites as aggregated positions. The occurrence of Pb2+ in watanabeite is probably related to the substitution Cu+ + (As,Sb)3+ = 2Me2+, where Me = Pb, Fe, Zn and formally divalent Cu. The relationships with tetrahedrite-group minerals are discussed on the basis of the refined structural model, highlighting possible crystal chemical implications of such relationships.

The new mineral tennantite-(Ni), Cu6(Cu4Ni2)As4S13, has been discovered from the Luobusa Chromitite, Tibet, southwestern China. Tennantite-(Ni) occurs as anhedral grains ranging from 2 to 20 μm in size. In reflected light microscopy, tennantite-(Ni) is isotropic and appears yellow-greenish grey. Reflectance data for Commission on Ore Mineralogy wavelengths in air for tennantite-(Ni) are: 31.0 (470 nm), 29.6 (546 nm), 29.6 (589 nm) and 29.3 (650 nm). Electron microprobe analysis for holotype material gave the empirical formula (on basis of total cations = 16 apfu): M(2)Cu6 M(1)[Cu4.00(Ni0.97Cu0.53Fe0.50)Σ2.00]Σ6.00X(3)(As2.94Sb1.06)Σ4S12.77. Tennantite-(Ni) is cubic, with space group I$\bar{ 4}$3m (#217), a =10.2957(9) Å, V = 1091.4(3) Å3 and Z = 2. By using single-crystal X-ray diffraction, the crystal structure has been determined and refined to a final R1 = 0.0423 on the basis of 163 independent reflections [Fo > 4σ (Fo)]. The calculated seven strongest powder X-ray diffraction lines [d in Å (I) (hkl)] are: 2.972 (100) (222), 1.820 (83) (440), 2.574 (28) (400), 1.552 (18) (622), 3.640 (10) (220), 1.880 (10) (521) and 1.287 (7) (800). Tennantite-(Ni) is isostructural with other tetrahedrite-group minerals, and nickel is hosted at the tetrahedrally coordinated M(1) site, along with Cu and minor Fe. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2021-018).

Argentotetrahedrite-(Cd), Ag6(Cu4Cd2)Sb4S13, has been approved as a new mineral species by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association using samples from Rudno nad Hronom, Slovak Republic. It occurs as anhedral grains up to 30 μm in size, steel-grey to black in colour, with a metallic lustre, in association with greenockite and other tetrahedrite-group minerals [argentotetrahedrite-(Zn) and tetrahedrite-(Zn)], earlier base-metal minerals, Ag sulfides and sulfosalts (acanthite, pyrargyrite and polybasite) and later galena. Argentotetrahedrite-(Cd) is isotropic, grey in colour, with a creamy tint and rapidly (tens of minutes) tarnishes to orange–brown. Reflectance data for Commission on Ore Mineralogy (COM) wavelengths in air are [λ (nm), R (%)]: 470, 30.4; 546, 30.3; 589, 30.3; and 650, 28.7. The chemical formula of the samples studied, recalculated on the basis of ΣMe = 16 atoms per formula unit, is: (Ag3.28Cu2.72)Ʃ6.00[Cu4(Cd1.68Fe0.27Zn0.16)]Ʃ6.11(Sb3.71As0.15)Ʃ3.86S12.79. Argentotetrahedrite-(Cd) is cubic, I$\bar{4}$3m, with a = 10.65(2) Å, V = 1208(4) Å3 and Z = 2. Argentotetrahedrite-(Cd) is isotypic with other members of the tetrahedrite group. The structural relationship between argentotetrahedrite-(Cd) and other members of the freibergite series are discussed and previous findings of this species are briefly reviewed.

Tennantite-(Cd), Cu10Cd2As4S13, was approved as a new mineral species from the Berenguela mining district, Pacajes Province, La Paz, Bolivia. It occurs as black metallic anhedral grains, up to 1 mm across, associated with baryte, montmorillonite and secondary Cd-sulfates (aldridgeite, niedermayrite and voudourisite). In reflected light, tennantite-(Cd) is isotropic and grey with brownish tints. Reflectance data for the four COM wavelengths in air are [λ (nm): R (%)]: 470: 30.0; 546: 30.1; 589: 28.2; and 650: 25.8. Electron microprobe analysis gave (in wt.% – average of 11 spot analyses): Cu 40.56(32), Ag 0.05(5), Fe 0.04(1), Zn 1.91(63), Cd 11.32(1.09), Hg 0.04(7), As 19.04(43), S 26.78(30), total 99.74(53). On the basis of ΣMe = 16 atoms per formula unit (apfu), the empirical formula of tennantite-(Cd) is Cu9.98Ag0.01Cd1.57Zn0.46Fe0.01As3.97S13.05. Tennantite-(Cd) is cubic, I$\bar{4}$3m, with unit-cell parameters a = 10.3088(2) Å, V = 1095.53(6) Å3 and Z = 2. Its crystal structure was refined by single-crystal X-ray diffraction data to a final R1 = 0.0152 on the basis of 359 unique reflections with Fo > 4σ(Fo) and 22 refined parameters. Tennantite-(Cd) is isotypic with other tetrahedrite-group minerals. Its crystal-chemistry is discussed and previous findings of Cd-rich tetrahedrite-group minerals are briefly reviewed.

Tennantite-(Cu), Cu12As4S13, was approved as a new mineral species from the Layo epithermal deposit, Castilla Province, Arequipa Department, Peru, where it occurs as black metallic anhedral grains, up to 0.1 mm across, replacing enargite and associated with chalcopyrite and vinciennite. In reflected light, tennantite-(Cu) is isotropic, grey with a bluish shade. Reflectance data for the four COM wavelengths in air are [λ (nm): R (%)]: 470: 29.1; 546: 28.4; 589: 27.4; and 650: 25.0. Electron microprobe analysis for holotype material gave (in wt.% – average of 10 spot analyses): Cu 49.32(27), Fe 2.20(12), Zn 0.09(2), Sn 0.03(5), As 19.45(43), Sb 1.94(10), Te 0.02(5), S 27.75(43), total 100.80(20). On the basis of (As + Sb + Te) = 4 atoms per formula unit (apfu), the empirical formula of tennantite-(Cu) is (Cu11.27Fe0.57Zn0.02)Σ11.86(As3.77Sb0.23)Σ4.00S12.57. Tennantite-(Cu) is cubic, I$\overline 4$3m, with unit-cell parameters a = 10.1710(10) Å, V = 1052.2(2) Å3 and Z = 2. Its crystal structure was refined by single-crystal X-ray diffraction data to a final R1 = 0.0178 on the basis of 263 unique reflections with Fo > 4σ(Fo) and 24 refined parameters. Tennantite-(Cu) is isotypic with other tetrahedrite-group minerals. Previous findings of tennantite-(Cu) are reported and some nomenclature issues, related to the Fe and Cu oxidation states, are discussed. At the Layo epithermal deposit, tennantite-(Cu) is the result of the replacement of enargite under decreasing $f_{{\rm S}_ 2}$ conditions.

Argentotetrahedrite-(Zn), Ag6(Cu4Zn2)Sb4S13, has been approved as a new mineral species by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA-CNMNC) using samples from Kremnica, Slovak Republic (hereafter KR), and Lengenbach, Switzerland (LE). Additionally, it was also identified at the small deposit of Zvěstov (Stříbrnice), Czech Republic (ZV). At the Slovak locality, it occurs as anhedral grains up to 0.1 mm in size, steel-grey in colour, with a metallic lustre, in association with ‘argentotennantite-(Fe)’ and tiny chalcopyrite grains in quartz gangue. At Lengenbach, it was found as domains of tristetrahedral crystal of tetrahedrite-(Zn), up to 1 mm in size, associated with dolomite. At Zvěstov, it occurs as irregular aggregates, up to 0.2 mm in size, partly rimmed by kenoargentotetrahedrite-(Fe). Argentotetrahedrite-(Zn) is isotropic, grey in colour, with blue-greenish tints. Reflectance data for COM wavelengths in air (KR sample) are [λ (nm), R (%)]: 470, 30.1; 546, 29.8; 589, 29.8; and 650, 28.3. Chemical formulae of the samples studied, recalculated on the basis of ΣMe = 16 apfu (atoms per formula unit), are: (Ag3.27Cu2.69)Σ5.96[Cu4.00(Zn1.69Fe0.23Cu0.05Cd0.02Hg0.01)Σ2.00](Sb3.86As0.17)Σ4.03S12.73 (KR), (Ag3.17Cu2.79)Σ5.96[Cu4.00(Zn1.55Cd0.23Fe0.16Cu0.05Hg0.01)Σ2.00](Sb3.71As0.32)Σ4.03S12.77 (LE) and (Ag3.27Cu2.67)Σ5.94[Cu4.00(Zn1.39Fe0.50Cu0.07Cd0.03Hg0.01)Σ2.00](Sb4.03As0.04)Σ4.07S13.08 (ZV). Argentotetrahedrite-(Zn) is cubic, I$\overline 4$3m, with a = 10.5505(10) Å, V = 1174.4(3) Å3 and Z = 2 (KR); a = 10.5155(13) Å and V = 1162.8(4) Å3 (LE); and a = 10.5663(12) Å and V = 1179.7 Å3 (ZV). The crystal structure of argentotetrahedrite-(Zn) has been refined by single-crystal X-ray diffraction data to a final R1 = 0.035 on the basis of 327 unique reflections with Fo > 4σ(Fo) and 22 refined parameters (sample KR). Argentotetrahedrite-(Zn) is isotypic with other members of the tetrahedrite group. The structural relationship between argentotetrahedrite-(Zn) and other members of the freibergite series are discussed and previous findings of this species are briefly reviewed.

Stibiogoldfieldite, Cu12(Sb2Te2)S13, was approved as a new mineral species from the Mohawk mine, Goldfield mining district, Esmeralda County, Nevada, USA. It occurs as metallic anhedral grains, dark grey in colour. It is associated with quartz, pyrite and an Ag–Bi–(S,Se) phase (holotype material) and with quartz, pyrite, calaverite, bismuthinite, bohdanowiczite, and the Ag–Bi–(S,Se) phase (cotype material). In reflected light, stibiogoldfieldite is isotropic, grey in colour, with indistinct brownish shade. Reflectance data in air [R (%)] are: 31.1 at 470 nm, 30.9 at 546 nm, 30.8 at 589 nm and 31.0 at 650 nm. Electron microprobe analysis for holotype material gave (in wt.% – average of 60 spot analyses): Cu 45.03(60), Ag 0.26(7), Fe 0.02(3), Zn 0.13(15), Sn 0.02(4), Pb 0.05(6), Sb 8.02(62), As 2.80(65), Bi 2.77(87), Te 15.15(1.24), S 24.50(32), Se 0.52(11), total 99.27(69). On the basis of (As + Sb + Te + Bi) = 4 atoms per formula unit (apfu), the empirical formula of stibiogoldfieldite is (Cu12.05Ag0.04Zn0.03Fe0.01)Σ12.13(Sb1.12As0.63Bi0.23Te2.02)Σ4.00(S12.99Se0.11)Σ13.10. Chemical data on an additional sample from the same locality (cotype material) gave the following results (in wt.% – average of 181 spot analyses): Cu 43.84(63), Ag 0.21(7), Sb 5.92(78), As 2.63(45), Te 20.07(1.19), S 25.13(53), Se 0.97(35), total 99.47(66). On the basis of (As + Sb + Te + Bi) = 4 apfu, the empirical formula of cotype material is (Cu11.30Ag0.03)Σ11.33(Sb0.80As0.57Bi0.06Te2.57)Σ4.00(S12.83Se0.20)Σ13.03. Stibiogoldfieldite is cubic, I$\overline 4$3m, with unit-cell parameters a = 10.3466(17) Å, V = 1107.6(5) Å3 and Z = 2 (holotype). Unit-cell parameters for the cotype sample are a = 10.3035(2) Å and V = 1093.83(7) Å3. The crystal structure of holotype stibiogoldfieldite was refined by single-crystal X-ray diffraction data to a final R1 = 0.032 on the basis of 285 reflections with Fo > 4σ(Fo) and 20 refined parameters. Stibiogoldfieldite is isotypic with other members of the tetrahedrite group.

Tennantite-(Hg), Cu6(Cu4Hg2)As4S13, was approved as a new mineral species (IMA2020-063) from the Lengenbach quarry, Imfeld, Binn Valley, Canton Valais, Switzerland. It was identified as an aggregate of black metallic tetrahedral crystals, less than 0.1 mm in size, intimately associated with sinnerite, and grown on realgar. In reflected light, tennantite-(Hg) is isotropic, grey in colour, with creamy tints. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 470: 29.1; 546: 29.1; 589: 28.5; 650: 27.7. Electron microprobe analysis gave (in wt.% – average of 7 spot analyses): Cu 32.57(42), Ag 6.38(19), Tl 0.29(14), Zn 0.04(5), Hg 17.94(2.27), Pb 0.70(51), As 17.83(61), Sb 0.34(8), S 24.10(41), total 100.19(1.04). The empirical formula of the sample studied, recalculated on the basis of ΣMe = 16 atoms per formula unit, is (Cu4.69Ag1.04Tl0.03)Σ5.76(Cu4.35Hg1.58Pb0.06Zn0.01)Σ6.00(As4.20Sb0.05)Σ4.25S13.26. Tennantite-(Hg) is cubic, I$\overline 4$3m, with a = 10.455(7) Å, V = 1143(2) Å3 and Z = 2. The crystal structure of tennantite-(Hg) has been refined by single-crystal X-ray diffraction data to a final R1 = 0.0897 on the basis of 214 unique reflections with Fo > 4σ(Fo) and 22 refined parameters. Tennantite-(Hg) is isotypic with other members of the tetrahedrite group. Mercury is hosted at the tetrahedrally coordinated M(1) site, in accord with the relatively long M(1)–S(1) distance (2.389 Å), similar to that observed in tetrahedrite-(Hg). Minor Ag is located at the triangularly-coordinated and split M(2) site. Other occurrences of tennantite-(Hg) are briefly reviewed and the Lengenbach finding is described within the framework of previous knowledge about the Hg mineralogy at this locality.

The crystal structure of pyrostilpnite from the Plaka mine, Lavrion Mining District, Greece, was refined in the space group P21/c to a final R1 index of 0.0283 on the basis of 2047 reflections with Fo > 4σ(Fo) and 65 refined parameters. Unit-cell parameters of the crystal examined are a = 6.8629(6), b = 15.8800(14), c = 6.2711(5) Å, β = 117.087(2)°, V = 608.48(9) Å3 and Z = 4. Chemical data agree with the stoichiometric formula Ag3SbS3. The crystal structure reported previously was confirmed, although a higher precision of refinement was achieved. It can be described as formed by {010} slabs running along c and connected along a through relatively longer Ag–S bonds. The analysis of the atomic displacement parameters together with a refinement with higher order tensors in the expression of the structure factors revealed no hint for pyrostilpnite as an ionic conductor. A historical background of the ‘ruby silvers’ is also reported.

Tetrahedrite-(Hg), Cu6(Cu4Hg2)Sb4S13, has been approved as a new mineral species using samples from Buca della Vena mine (hereafter BdV), Italy, Jedová hora (Jh), Czech Republic and Rožňava (R), Slovakia. It occurs as anhedral grains or as tetrahedral crystals, black in colour, with metallic lustre. At BdV it is associated with cinnabar and chalcostibite in dolomite veins. At Jh, tetrahedrite-(Hg) is associated with baryte and chalcopyrite in quartz–siderite–dolomite veins; at R it is associated with quartz in siderite–quartz veins. Tetrahedrite-(Hg) is isotropic, greyish-white in colour, with creamy tints. Minimum and maximum reflectance data for Commission on Ore Mineralogy wavelengths in air (BdV sample), R in %) are 32.5 at 420 nm; 32.9 at 546 nm; 33.2 at 589 nm; and 30.9 at 650 nm. Chemical formulae of the samples studied, recalculated on the basis of 4 (As + Sb + Bi) atoms per formula unit, are: (Cu9.44Ag0.07)Σ9.51(Hg1.64Zn0.36Fe0.06)Σ2.06Sb4(S12.69Se0.01)Σ12.70 (BdV), Cu9.69(Hg1.75Fe0.25Zn0.06)Σ2.06(Sb3.94As0.06)S12.87 (Jh) and (Cu9.76Ag0.04) Σ9.80(Hg1.83Fe0.15Zn0.10)Σ2.08(Sb3.17As0.58Bi0.25)S13.01 (R). Tetrahedrite-(Hg) is cubic, I$\overline 4 $3m, with a = 10.5057(8) Å, V = 1159.5(3) Å3 and Z = 2 (BdV). Unit-cell parameters for the other two samples are a = 10.4939(1) Å and V = 1155.61(5) Å3 (Jh) and a = 10.4725(1) Å and V = 1148.55(6) Å3 (R). The crystal structure of tetrahedrite-(Hg) has been refined by single-crystal X-ray diffraction data to a final R1 = 0.019 on the basis of 335 reflections with Fo > 4σ(Fo) and 20 refined parameters. Tetrahedrite-(Hg) is isotypic with other members of the tetrahedrite group. Mercury is hosted at the tetrahedrally coordinated M(1) site, along with minor Zn and Fe. The occurrence of Hg at this position agrees both with the relatively large M(1)–S(1) bond distance (2.393 Å) and the refined site scattering. Previous occurrences of Hg-rich tetrahedrite and tetrahedrite-(Hg) are reviewed, and its relations with other Hg sulfosalts are discussed.

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.

Barikaite, ideally Pb10Ag3(Sb8As11)Σ19S40, is a new mineral species from the Barika Au-Ag deposit, Azarbaijan Province, western Iran. It was formed in fractures developed in silica bands situated in massive banded pyrite and baryte ores. These fractures house veinlets that contain a number of Ag-As-Sb-Pb-rich sulfosalts, tetrahedrite-tennantite, realgar, pyrite and electrum. Barikaite appears as inclusions in guettardite. The mineral is opaque, greyish black with a metallic lustre; it is brittle without any discernible cleavage. In reflected light barikaite is greyish white, pleochroism is distinct, white to dark grey. Internal reflections are absent. In crossed polars, anisotropism is distinct with rotation tints in shades of grey. The reflectance data (%, in air) are: 37.0, 39.3 at 470 nm, 34.1, 36.9 at 546 nm, 33.1, 36.2 at 589 nm and 31.3, 34.1 at 650 nm. The Mohs hardness is 3–3½, microhardness VHN50 exhibits the range 192 – 212, with a mean value of 200 kg mm–2. The average results of five electron-microprobe analyses in a grain are (in wt.%): Pb 35.77(33), Ag 5.8(1), Tl 0.15(08), Sb 18.33(09), As 15.64(16), S 24.00(15), total 99.69(10) wt.%, corresponding to Pb9.31Ag2.90Tl0.04(Sb8.12As11.26)Σ19.36S40.37 (on the basis of 32Me + 40S = 72 a.p.f.u.). The simplified formula, Pb10Ag3(Sb8As11)Σ19S40, is in accordance with the results of a crystal-structure analysis, and requires Pb 37.89, Ag 5.91, Sb 17.79, As 15.05 and S 23.42 (wt.%). The variation of chemical composition is minor, the empirical formula ranging from Pb10.39Ag2.32Tl0.02Sb7.52As11.27S40.49 to Pb9.24Ag2.93Tl0.04Sb8.13As11.35S40.31. Barikaite has monoclinic symmetry, space group P21/n and unit-cell parameters a 8.5325(7) Å, b 8.0749(7) Å, c 24.828(2) Å, and b 99.077(6)o, Z = 1. Calculated density for the empirical formula is 5.34 (g cm–3). The strongest eight lines in the (calculated) powder-diffraction pattern [d in Å(I)(hkl)] are: 3.835(63)(022), 3.646(100)(016), 3.441(60)(212), 3.408(62)(14), 2.972(66)(16), 2.769(91)(222), 2.752(78)(24) and 2.133(54)(402). Barikaite is the N = 4 member of the sartorite homologous series with a near-equal role of As and Sb, which have an ordered distribution pattern in the structure. It is a close homeotype of rathite and more distantly related to dufrénoysite (both distinct, pure arsenian N = 4 members) and it completes the spectrum of Sb-rich members of the sartorite homologous series. The new mineral and its name have been approved by the IMA-CNMNC (IMA 2012-055).

A third world occurrence of rouxelite, ideally Cu2HgPb22Sb28S64(O,S)2, has been identified from the baryte-pyrite-Fe oxides ore of Monte Arsiccio mine, near Sant’Anna di Stazzema (Apuan Alps, Tuscany, Italy). Rouxelite occurs as mm-sized acicular crystals, black in colour, with bluish-violet iridescence, in vugs of carbonate + baryte + quartz veins embedded in dolostones from the Sant’Olga tunnel. It is associated with Tl-bearing chovanite, sphalerite and valentinite. Its X-ray powder diffraction pattern gives unit-cell parameters a = 43.10(2), b = 4.060(2), c = 37.88(2) Å, β = 117.33(2)°, V = 5889(5) Å3. Electron-microprobe data reveal a complex chemistry, with additional minor elements (wt.%): Tl (0.6–1.7), Ag (0.4–0.6), As (0.2–0.6) and Bi (≤0.05). This indicates a widespread substitution of Hg by Ag, according to Hg + Pb = Ag + Sb and incorporation of Tl, with some Ag, according to 2Pb = Sb + (Tl, Ag). The occurrence of mixed (Hg, Ag) and (Hg, Cu) sites in natural sulfides and sulfosalts is briefly reviewed. The Tl-content of the samples studied is a characteristic fingerprint agreeing with the Tl-rich nature of the mineral assemblage from Monte Arsiccio. Rouxelite therefore constitutes a new example of a Tl-bearing sulfosalt.

The new mineral species arsiccioite, AgHg2TlAs2S6, was discovered in the baryte-pyrite-iron oxide ore deposit exploited at the Monte Arsiccio mine, near Sant’Anna di Stazzema (Apuan Alps, Tuscany, Italy). It occurs as anhedral grains scattered in microcrystalline baryte, associated with cinnabar, laffittite, protochabournéite, pyrite, realgar, Hg-bearing sphalerite and stibnite. Arsiccioite is red, with a metallic to sub-metallic lustre. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 471.1: 29.0/29.4; 548.3: 27.6/28.3; 586.6: 26.1/26.5; 652.3: 24.2/24.6. Electron microprobe analyses give (wt.%): Cu 0.78(6), Ag 8.68(21), Zn 0.47(27), Fe 0.04(1), Hg 35.36(87), Cd 0.20(5), Tl 18.79(33), As 10.77(19), Sb 4.75(10), S 18.08(21), Se 0.07(5), total 97.99(44). On the basis of ΣMe = 6 a.p.f.u., the chemical formula is Ag0.87(2)Cu0.13(1)Zn0.08(4)Fe0.01(1)Hg1.91(5)Cd0.02(1)Tl1.00(2) (As1.56(2)Sb0.42(1))S1.98S6.12(6)Se0.01(1). Arsiccioite is tetragonal, I2m, with a 10.1386(6), c 11.3441(5) Å, V 1166.1(2) Å3, Z = 4. The main diffraction lines of the powder diagram are [d(in Å), visually estimated intensity, hkl]: 4.195, m, 211; 3.542, m, 103; 3.025, vs, 222; 2.636, m, 114; 2.518, s, 400 and 303. The crystal structure of arsiccioite has been refined by single-crystal X-ray data to a final R1 = 0.030, on the basis of 893 observed reflections. It shows a three dimensional framework of (Hg,Ag)- centred tetrahedra (1 M1 + 2 M2), with channels parallel to [001] hosting TlS6 and (As,Sb)S3 disymmetric polyhedra. Arsiccioite is derived from its isotype routhierite M1CuM2Hg2TlAs2S6 through the double heterovalent substitution M1Cu+ + M2Hg2+ → M1Hg2+ + M2Ag+. This substitution obeys a steric constraint, with Ag+, the largest cation relative to Hg2+ and Cu+, entering the largest M2 site. The ideal crystal chemical formula of arsiccioite is M1HgM2(Hg0.5Ag0.5)2TlAs2S6. The crystal chemistry of the routhierite isotypic series is discussed. Finally, the distribution of Hg ore minerals in the Apuan Alps is reviewed.

The new mineral species carducciite, (AgSb)Pb6(As,Sb)8S20, has been discovered in the baryte-pyrite- (Pb-Ag-Zn) deposit of the Pollone mine, near Valdicastello Carducci, Apuan Alps, Tuscany, Italy. It occurs as black metallic prismatic crystals, up to 0.5 mm long, associated with pyrite and sterryite. Its Vickers hardness (VHN10) is 61 kg/mm2 (range: 52–66), corresponding to a Mohs hardness of ~2½–3. In reflected light, carducciite is dark grey in colour, moderately bireflectant; internal reflections are very weak and deep red in colour. Reflectance percentages for the four COM wavelengths [Rmin, Rmax (%) (λ)] are: 35.8, 40.8 (471.1 nm), 33.7, 39.0 (548.3 nm), 32.7, 37.6 (586.6 nm) and 30.4, 35.1 (652.3 nm). Electron microprobe analysis gives (wt.% – mean of six analyses): Ag 3.55(12), Tl 0.13(3), Pb 41.90(42), Sb 17.79(19), As 12.41(14), S 22.10(17), total 97.9(6). On the basis of ΣMe = 16 a.p.f.u., the chemical formula is Ag0.96Tl0.02Pb5.91As4.84Sb4.27S20.14. The main diffraction lines, corresponding to multiple hkl indices, are (relative visual intensity): 3.689 (s), 3.416 (s), 3.125 (s), 2.989 (s), 2.894 (s), 2.753 (vs), 2.250 (s). The crystal-structure study gives a monoclinic unit cell, space group P21/c, with a 8.4909(3), b 8.0227(3), c 25.3957(9) Å, β 100.382(2)°, V 1701.63(11) Å3, Z = 2. The crystal structure has been solved and refined to a final R1 = 0.063 on the basis of 4137 observed reflections. It can be described within the framework of the sartorite homologous series, as formed by chemically twinned layers of the dufrénoysite type. The simplified idealized structural formula, based on 20 sulfur atoms, can ideally be written as (AgSb)Pb6(As,Sb)Σ=8S20. Carducciite is an (Ag,Sb)-rich homeotype of dufrénoysite, stabilized by the complete coupled substitution 2 Pb2+ = Ag+ + Sb3+ on a specific site of the crystal structure. Together with barikaite, it belongs to the rathite sub-group of P21/c homeotypes of dufrénoysite, of which the crystal chemistry is discussed. The distribution of Ag, coupled with As or Sb on specific sites, appears to be the main criterion for the distinction between the three species of this sub-group.

Boscardinite, ideally TlPb4(Sb7As2)∑9S18, has been described recently as a new homeotypic derivative of baumhauerite, found at Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. New findings of boscardinite in different mineral associations of this deposit have allowed the collection of new crystal-chemical data. Electron-microprobe analysis of the crystal used for the single-crystal X-ray diffraction study gave (in wt.%): Ag 1.81(5), Tl 12.60(21), Pb 17.99(12), Hg 0.14(5), As 9.36(12), Sb 33.60(27), S 23.41(30),Cl 0.06(1), total 98.97(100). On the basis of ∑Me = 14 apfu, it corresponds to Ag0.42Tl1.52Pb2.14Hg0.02 (Sb6.82As3.08)∑9.90S18.04Cl0.04. With respect to the type specimen, these new findings are characterized by a strong Pb depletion, coupled with higher Tl contents, and a significant As enrichment. The single-crystal X-ray diffraction study of this (Tl,As)-enriched boscardinite confirms the structural features described for the type sample. The unit-cell parameters are a = 8.1017(4), b = 8.6597(4), c = 22.5574(10) Å, α = 90.666(2), β = 97.242(2), γ = 90.850(2)°, V = 1569.63(12) Å3, space group P̄1. The crystal structure was refined down to R1 = 0.0285 on the basis of 6582 reflections with Fo > 4σ(Fo). Arsenic is dominant in three MeS3 sites, compared to one in type boscardinite. The main As-enrichment is observed in the sartorite-type sub-layer. Owing to this chemical peculiarity, (Tl, As)-rich boscardinite shows alternation, along b, of Sb-rich sites and As-rich sites; this feature represents the main factor controlling the 8 Å superstructure. The chemical variability of boscardinite is discussed; the Ag increase observed here gets closer to stoichiometric AgTl3Pb4(Sb14As6)∑20S36 (Z = 1), against possible extension up to AgTl2Pb6(Sb15As4)∑19S36 for type boscardinite.

The new mineral species ralphcannonite, AgZn2TlAs2S6, was discovered in the Lengenbach quarry, Binn Valley, Wallis, Switzerland. It occurs as metallic black equant, isometric to prismatic crystals, up to 50 μm, associated with dufrénoysite, hatchite, realgar and baryte. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 471.1: 25.8/27.1; 548.3: 25.2/26.6; 586.6: 24.6/25.8; 652.3: 23.9/24.8. Electron microprobe analyses give (wt.%): Cu 2.01(6), Ag 8.50(16), Zn 10.94(20), Fe 3.25(8), Hg 7.92(12), Tl 24.58(26), As 18.36(19), Sb 0.17(4), S 24.03(21), total 99.76(71). On the basis of 12 atoms per formula unit, the chemical formula of ralphcannonite is Ag0.63(2)Cu0.25(2)Zn1.35(5)Fe0.47(1)Hg0.32(2)Tl0.97(3)[As1.97(6)Sb0.01(1)]Σ1.98(5)S6.03(8). The new mineral is tetragonal, space group I42m, with a = 9.861 (2), c = 11.125(3) Å, V = 1081.8(4) Å3, Z = 4. The main diffraction lines of the calculated powder diagram are [d (in Å), intensity, hkl]: 4.100, 85, 211; 3.471, 40, 103; 2.954, 100, 222; 2.465, 24, 400; 2.460, 39, 303. The crystal structure of ralphcannonite has been refined by X-ray single-crystal data to a final R1 = 0.030, on the basis of 140 observed reflections [Fo > 4σ(Fo)]. It shows a three dimensional framework of (Ag,Zn)-centred tetrahedra (1 M1 + 2 M2), with channels parallel to [001] hosting TlS6 and (As,Sb)S3 disymmetric polyhedra. Ralphcannonite is derived from its isotype routhierite M1CuM2Hg2TlAs2S6 through the double heterovalent substitution M1Cu+ + M2Hg2+ → M1Zn2+ + M2Ag+. This substitution obeys a steric constraint, with Ag+, the largest cation relative to Zn2+ and Cu+, entering the largest M2 site, as observed in arsiccioite. The ideal crystal-chemical formula of ralphcannonite is M1ZnM2(Zn0.5Ag0.5)2TlAs2S6.

The new mineral species meerschautite, ideally (Ag,Cu)5.5Pb42.4(Sb,As)45.1S112O0.8, has been discovered in the baryte + pyrite ± (Pb-Zn-Ag) deposit of the Pollone mine, near Valdicastello Carducci, Apuan Alps, Tuscany, Italy. It occurs as black prismatic crystals, striated along [100], up to 2 mm long and 0.5 mm thick, associated with baryte, boulangerite, pyrite, quartz and sphalerite. Meerschautite is opaque with a metallic lustre and shows a black streak. In reflected light, meerschautite is white in colour, weakly bireflectant and non pleochroic. With crossed polars, it is distinctly anisotropic with grey to dark grey rotation tints with brownish and greenish shades. Reflectance percentages for COM wavelengths [λ (nm), Rair (%)] are: 470: 39.7/41.4; 546: 38.3/39.9; 589: 37.4/39.0; 650: 35.8/37.2. Electron-microprobe data collected on two different samples gave (wt.%): Cu 0.22, Ag 3.15, Tl 0.07, Pb 48.54, Sb 25.41, As 2.82, S 19.74, Se 0.14, Cl 0.03, sum 100.12 (# 1) and Cu 0.22, Ag 3.04, Tl 0.13, Pb 48.53, Sb 25.40, As 2.93, Bi 0.06, S 19.82, Se 0.13, Cl 0.05, sum 100.31 (# 2). On the basis of 112 anions (S+Se+Cl) per formula unit, the empirical formulae are (Ag5.29Cu0.63)∑5.92(Pb42.43Tl0.06)∑42.49(Sb37.80As6.82)∑44.62(S111.53Se0.32Cl0.15)∑112 (# 1) and (Ag5.08Cu0.62)∑5.70(Pb42.22Tl0.12)∑42.34(Sb37.61As7.07Bi0.05)∑44.73(S111.45Se0.30Cl0.25)∑112 (# 2). Main diffraction lines, corresponding to multiple hkl indices, are [d in Å (relative visual intensity)]: 3.762 (m), 3.663 (s), 3.334 (vs), 3.244 (s), 3.016 (m), 2.968 (m), 2.902 (m), 2.072 (ms). The crystal structure study gave a monoclinic unit cell, space group P21, with a = 8.2393(1), b = 43.6015(13), c = 28.3688(8) Å, β = 94.128(2)°, V = 10164.93(2) Å3, Z = 2. The crystal structure has been solved and refined to a final R1 = 0.122 on the basis of 49,037 observed reflections. The structure is based on two building blocks, both formed by a complex column with a pseudotrigonal Pb6S12 core and two arms of unequal lengths (short and long arms, respectively). Two different kinds of short arms occur in meerschautite. One is an Ag-rich arm, whereas the other shows localized Sb–O–Sb bonds. Meerschautite is an expanded derivative of owyheeite and has quasi-homeotypic relationships with sterryite and parasterryite.