A new occurrence of austinite, CaZnAsO4(OH), conichalcite, CaCuAsO4(OH), and zincolivenite, CuZnAsO4(OH), is described from the Tripi mine, Peloritani Mountains, Sicily, Italy. These species have been observed in euhedral crystals in vugs of a calcite vein and were characterised using single-crystal X-ray diffraction, electron microprobe analysis and micro-Raman spectroscopy. Austinite and conichalcite have isotypic relations, both crystallising in space group P212121. Unit-cell parameters of austinite are a = 7.4931(5), b = 9.0256(6), c = 5.9155(4) Å, V = 400.06(5) Å3; its crystal structure was refined on the basis of 1210 unique reflections with Fo > 4σ(Fo) and 77 least-square parameters to R1 = 0.0236. Conichalcite has unit-cell parameters a = 7.419(10), b = 9.111(11), c = 5.867(7) Å and V = 396.6(1.4) Å3; the diffraction quality of its available grains was not good enough to allow a high-quality structural refinement. Chemical formulae of austinite and conichalcite are Ca1.04(1)Zn0.86(4)Cu0.09(4)As0.98(2)P0.02(1)O4(OH)0.98 and Ca0.98(1)Fe2+0.02(4)Cu0.69(10)Zn0.30(6)As0.97(2)P0.03(1)O4(OH)0.98, respectively. The new chemical data on the austinite–conichalcite isotypic pair, coupled with previous analyses, supports a possible miscibility gap between the compositions (Zn0.25Cu0.75) and (Zn0.50Cu0.50). Zincolivenite has unit-cell parameters a = 8.4594(9), b = 8.5324(8), c = 5.9893(6) Å, V = 432.30(12) Å3 and space group Pnnm; its crystal structure was refined to R1 = 0.0230 for 523 unique reflections with Fo > 4σ(Fo) and 47 least-square parameters. Its chemical composition is Cu0.73(5)Zn1.25(5)As1.01(1)O4(OH)1.01. The refinement of the crystal structure supports the ordering of Cu and Zn in two different crystallographic sites. Micro-Raman spectra of austinite, conichalcite and zincolivenite are discussed, with a focus on the O–H stretching region where local Zn and Cu arrangements affect the position of Raman bands in zincolivenite. These arsenates probably play an environmental role in the Peloritani area, where the occurrence of high contents of some potentially toxic elements in soils and stream sediments has been reported.

Vrančiceite is a new mineral species discovered in a sample collected from the old mine dumps of the abandoned Vrančice deposit near Příbram, central Bohemia, Czech Republic. Vrančiceite occurs as rare anhedral grains, up to 100 μm in size, in a calcite gangue, associated with cinnabar, djurleite, galena and hedyphane. Vrančiceite is black, with metallic lustre. Mohs hardness is ca. 2–3, calculated density is 6.652 g.cm–3. In reflected light, vrančiceite is light grey with a yellowish shade; bireflectance, pleochroism and anisotropy are all weak. Internal reflections were not observed. Reflectance values for the four Commission on Ore Mineralogy wavelengths of vrančiceite in air [Rmax, Rmin (%) (λ in nm)] are: 33.6, 31.2 (470); 33.9, 30.6 (546); 31.1, 30.0 (589); and 32.1, 29.1 (650). The empirical formula, based on electron-microprobe analyses, is Cu10.11(4)Ag0.01(1)Hg2.87(4)Sb0.01(1)Bi0.01(1)S7.99(8). The ideal formula is Cu10Hg3S8 (Z = 2), which requires (in wt.%) Cu 42.54, Hg 40.29 and S 17.17, total 100.00. Vrančiceite is triclinic, P$\bar{1}$, with unit-cell parameters a = 7.9681(2), b = 9.7452(3), c = 10.0710(3) Å, α = 77.759(1), β = 76.990(1), γ = 79.422(1)°, V = 737.01(4) Å3 and Z = 2. The strongest reflections of the calculated powder X-ray diffraction pattern [d, Å (I) hkl] are: 3.354 (76) $\bar{2}$01, 3.111 (68) 222, 2.833 (100) 213, 2.733 (93) 231, 2.705 (76) 2$\bar{2}$1 and 2.647 (71) $\bar{2}\bar{1}$2. According to the single-crystal X-ray diffraction data (R1 = 0.0262), the crystal structure of vrančiceite can be described as comprising Cu–S layers, connected through CuS3 polyhedra, giving rise to a three-dimensional framework with channels running along the a axis and hosting linearly coordinated Hg atoms. Structural relations with gortdrumite are discussed. Vrančiceite is named after its type locality, the Vrančice deposit near Příbram. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2022–114).

Piccoliite, ideally NaCaMn3+2(AsO4)2O(OH), is a new mineral discovered in the Fe–Mn ore hosted in metaquartzites of the Montaldo di Mondovì mine, Corsaglia Valley, Cuneo Province, Piedmont, Italy. It occurs as small and rare black crystals and aggregates hosted by a matrix of quartz, associated with calcite and berzeliite/manganberzeliite. It has been also found in the Valletta mine near Canosio, Maira Valley, Cuneo Province, Piedmont, Italy, where it occurs embedded in quartz associated with grandaite, hematite, tilasite/adelite and rarely thorianite. The mineral is opaque (thin splinters may be very dark red), with brown streak and has a resinous to vitreous lustre. It is brittle with irregular fracture. No cleavage has been observed. The measured Mohs hardness is ~5–5.5. Piccoliite is non fluorescent. The calculated density is 4.08 g⋅cm–3. Chemical spot analyses by electron microprobe analysis using wavelength dispersive spectroscopy resulted in the empirical formula (based on 10 anions per formula unit) (Na0.64Ca0.35)Σ0.99(Ca0.75Na0.24)Σ0.99(Mn3+1.08Fe3+0.59Mg0.20Ca0.10)Σ1.97(As2.03V0.03Si0.01)Σ2.07O9(OH) and (Na0.53Ca0.47)Σ1.00(Ca0.76Na0.23Sr0.01)Σ1.00(Mn3+0.63Fe3+0.49Mg0.48Mn4+0.34Ca0.06)Σ2.00(As1.97P0.01Si0.01)Σ1.99O9(OH) for the Montaldo di Mondovì and Valletta samples, respectively. The mineral is orthorhombic, Pbcm, with single-crystal unit-cell parameters a = 8.8761(9), b = 7.5190(8), c = 11.689(1) Å and V = 780.1(1) Å3 (Montaldo di Mondovì sample) and a = 8.8889(2), b = 7.5269(1), c = 11.6795(2) Å, V = 781.43(2) Å3 (Valletta sample) with Z = 4. The seven strongest powder X-ray diffraction lines for the sample from Montaldo di Mondovì are [d Å (Irel; hkl)]: 4.85 (57; 102), 3.470 (59; 120, 113), 3.167 (100; 022), 2.742 (30; 310, 213), 2.683 (53; 311, 023), 2.580 (50; 222, 114) and 2.325 (19; 320, 214, 223). The crystal structure (R1 = 0.0250 for 1554 unique reflections for the Montaldo di Mondovì sample and 0.0260 for 3242 unique reflections for the Valletta sample) has MnO5(OH) octahedra forming edge-shared dimers; these dimers are connected through corner-sharing, forming two-up-two-down [[6]M2([4]TO4)4φ2] chains [M = Mn; T = As; φ = O(OH)] running along [001]. These chains are bonded in the a and b directions by sharing corners with AsO4 tetrahedra, giving rise to a framework of tetrahedra and octahedra hosting seven-coordinated Ca2+ and Na+ cations. The crystal structure of piccoliite is closely related to that of pilawite-(Y) as well as to carminite-group minerals that also show the same type of chains but with different linkage. The mineral is named after the mineral collectors Gian Paolo Piccoli and Gian Carlo Piccoli (father and son) (1926–1996 and b. 1953, respectively), the latter having discovered the type material at the Montaldo di Mondovì mine.

Following the identification of a new occurrence of melanostibite from the Apuan Alps, the crystal chemistry of this mineral has been re-examined using specimens from its type locality, Sjögruvan, Örebro County, Sweden, and from the new occurrence, the Scortico–Ravazzone Mn ore deposit, Apuan Alps, Tuscany, Italy. Both specimens were examined through electron microprobe analysis, micro-Raman spectroscopy and single-crystal X-ray diffraction data; Mössbauer spectroscopy was used for the Swedish specimen. Electron microprobe data indicate a close to ideal composition Mn2Fe3+Sb5+O6 for both samples, whereas Mössbauer spectroscopy confirmed the trivalent oxidation state of Fe. Single-crystal X-ray diffraction for the Swedish and Italian specimens points to the acentric nature of melanostibite, space group R3. Refined unit-cell parameters of melanostibite from Scortico–Ravazzone and Sjögruvan are a = 5.2351(3), c = 14.3645(8) Å, V = 340.93(4) Å3, and a = 5.2314(2), c = 14.3518(8) Å, V = 340.15(3) Å3, respectively. Melanostibite is an homeotypic derivative of pyrophanite.

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.

Uvite, CaMg3(Al5Mg)(Si6O18)(BO3)3(OH)3(OH), is a new mineral of the tourmaline supergroup. It occurs in the Facciatoia quarry, San Piero in Campo, Elba Island, Italy (42°45′04.55″N, 10°12′50.89″E) at the centre of a narrow (2–3 cm wide) vein composed of aggregates of dark brown to black tourmaline, penetrating (magnesite + dolomite)-rich hydrothermally altered metaserpentinite. Crystals are euhedral and up to 1 cm in size, brown with a vitreous lustre, conchoidal fracture and grey streak. Uvite has a Mohs hardness of ~7½, a calculated density of 3.115 g/cm3 and is uniaxial (–). Uvite has trigonal symmetry, space group R3m, a = 15.9519(10) Å, c = 7.2222(5) Å, V = 1597.3(1) Å3 and Z = 3. The crystal structure was refined to R1 = 1.77% using 1666 unique reflections collected with MoKα X-rays. Crystal-chemical analysis resulted in the empirical crystal-chemical formula $^X ({\rm Ca}_{0.61}{\rm Na}_{{0.35}} \square_{{0.04}})_{\Sigma 1.00}{}^{Y} \left( {{\rm Mg}_{1.50}{\rm Fe}^{2 + }_{0.47} {\rm Al}_{0.71}{\rm Fe}^{3 + }_{0.14} {\rm Ti}_{0.18}} \right)_{\Sigma 3.00}$${}^{Z} \left( {{\rm Al}_{4.54}{\rm Fe}^{3 + }_{0.18} {\rm V}^{3 + }_{0.02} {\rm Mg}_{1.27}} \right)_{\Sigma 6.00}{}^{T}\left[ {{\left( {{\rm Si}_{5.90}{\rm Al}_{0.10}} \right)}_{\Sigma 6.00}{\rm O}_{18}} \right]{\rm } \left( {\rm BO_3} \right)_3^{} {^{\rm O(3)}}\left( {\rm OH} \right)_3{}^{{\rm O}\left( 1 \right)} [\left( {\rm OH} \right)_{0.55}{\rm F}_{0.05}{\rm O}_{0.40}]_{\Sigma 1.00}$

which recast in its ordered form for classification purposes is:

$$\eqalign{& ^{\rm X} ({\rm Ca}_{0.61}{\rm Na}_{0.35}\squ _{0.04})_{\Sigma 1.00}{}^{\rm Y} \left( {{\rm Mg}_{2.35}{\rm Fe}^{2 + }_{0.47} {\rm Ti}_{0.18}} \right)_{\Sigma 3.00} \cr & {}^{\rm Z} \left( {{\rm Al}_{5.25}{\rm Fe}^{3 + }_{0.32} {\rm V}^{3 + }_{0.02} {\rm Mg}_{0.42}} \right)_{\Sigma 6.00}{}^{\rm T} \left[ {{\left( {{\rm Si}_{5.90}{\rm Al}_{0.10}} \right)}_{\Sigma 6.00}{\rm O}_{18}} \right]{\rm }\left( {\rm BO_3} \right)_3{}^{\rm V} \left( {\rm OH} \right)_3{}^{\rm W} [\left( {\rm OH} \right)_{0.55}{\rm F}_{0.05}{\rm O}_{0.40}]_{\Sigma 1.00}}$$

Historical samples of branchite, described by the Tuscan naturalist Paolo Savi (1798–1871) at the end of the 1830s, were re-examined through single-crystal X-ray diffraction, showing their identity with hartite, C20H34, a hydrocarbon mineral described by Haidinger in 1841. The refined unit-cell parameters are a = 11.4116(7), b = 20.9688(12), c = 7.4100(4) Å, α = 93.947(2), β = 100.734(2), γ = 80.524(2)°, V = 1716.99(17) Å3 and Z = 4; space group P1. The crystal structure was solved and refined up to R1 = 0.0424 for 13512 reflections with Fo > 4σ(Fo) and 1265 refined parameters. As the name ‘branchite’ has priority over ‘hartite’, the reinstatement of the former name and the discreditation of the latter were approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA–CNMNC). Branchite is one of only eleven minerals formed by C and H listed in the official IMA List of Minerals. The type locality of branchite is the Botro di Lavajano, Monte Vaso, Chianni, Pisa, Tuscany, Italy. Neotype material is kept in the Natural History Museum of the Pisa University under catalogue number 14426.

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.

A new occurrence of kintoreite, ideally PbFe3(PO4)(PO3OH)(OH)6, is described from the Tripi mine, Alì, Peloritani Mountains, northeastern Sicily, Italy. Kintoreite occurs as yellow equant crystals, up to 0.05 mm in size, on quartz, associated with another alunite-supergroup mineral currently under study. The studied grains of kintoreite are chemically zoned, showing the occurrence of two distinct domains. Electron microprobe analyses gave (in wt.%): SO3 5.47(27), P2O5 17.55(14), Al2O3 7.81(35), Fe2O3 23.81(44), PbO 35.11(41), H2Ocalc 9.93, total 99.68 (darker domains) and SO3 6.03(5), P2O5 16.66(23), Al2O3 4.22(2), Fe2O3 27.31(6), PbO 33.78(22), H2Ocalc 10.25, total 98.25 (brighter domains). On the basis of 14 O atoms per formula unit (apfu) and (P+S) = 2 apfu, the darker and brighter domains have chemical formula Pb1.00(Fe3+1.89Al0.97)Σ2.86[P1.57S0.43O7.43(OH)0.57][(OH)5.58(H2O)0.42]Σ6.00 and Pb0.98(Fe3+2.21Al0.53)Σ2.74[P1.51S0.49O7.49(OH)0.51][(OH)5.18(H2O)0.82]Σ6.00, respectively. Single-crystal X-ray diffraction was performed on a grain extracted from the same sample. Unit-cell parameters are a = 7.2191(10), c = 16.834(3) Å, V = 759.8(3) Å3 and Z = 3; space group R$\bar{3}$m. The crystal structure was refined on the basis of 226 unique reflections with Fo > 4σ(Fo) and 31 least-square parameters to R1 = 0.0415. Kintoreite is isotypic with other alunite-supergroup minerals. Micro-Raman spectroscopy suggests the possible occurrence of H2O groups, supporting the possible protonation of (OH) groups as a charge-balance mechanism in this mineral. Kintoreite may play an environmental role in the Alì area, where previous authors detected high concentrations of potentially toxic elements in soils.

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 new mineral, zvěstovite-(Zn), ideally Ag6(Ag4Zn2)As4S13, was found in quartz–baryte gangue at the mine dump of the abandoned small deposit of Zvěstov, central Bohemia, Czech Republic. Zvěstovite-(Zn) is associated with tennantite-(Zn), tetrahedrite-(Zn), argentotennantite-(Zn), acanthite and supergene azurite and malachite. The new mineral occurs as rare relic anhedral grains rimmed by acanthite, up to 100 μm in size. Zvěstovite-(Zn) is grey, Mohs hardness is ca. 3½–4, in agreement with other members of the tetrahedrite group; the calculated density is 5.16 g.cm–3. In reflected light, zvěstovite-(Zn) is grey with a greenish tint, without bireflectance, pleochroism or anisotropy. Deep red internal reflections are ubiquitous. Reflectance values of zvěstovite-(Zn) in air (R%) are: 28.5 at 470 nm, 26.9 at 546 nm, 25.5 at 589 nm and 23.8 at 650 nm. The empirical formula for zvěstovite-(Zn), based on electron-microprobe analyses (n = 4), is Ag6.27[(Ag3.90Cu0.38)Σ4.28(Zn1.60Fe0.09Cd0.03)Σ1.72]Σ6.00(As2.26Sb1.48)Σ3.74S12.50. The ideal formula is Ag6(Ag4Zn2)As4S13, which requires (in wt.%) Ag 56.01, Zn 6.79, As 15.56 and S 21.64, total 100.00. Zvěstovite-(Zn) is cubic, I$\bar{4}$3m, with unit-cell parameters: a = 10.850(2) Å, V = 1277.3(8) Å3 and Z = 2. The strongest reflections of the calculated powder X-ray diffraction pattern [d, Å (I) (hkl)] are: 3.1321(100) (222), 2.7125(21) (400), 1.9809(11) (521), 1.9180(31) (440) and 1.6357(15) (622). According to the single-crystal X-ray diffraction data (Robs = 0.051), the crystal structure of zvěstovite-(Zn) agrees with the general features of the members of the tetrahedrite group. Zvěstovite-(Zn) is named after its type locality, Zvěstov; the suffix indicates the dominant divalent C-constituent, according to the approved nomenclature of the tetrahedrite group. It is the As-isotype of rozhdestvenskayaite-(Zn). The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2020-061).

The new mineral bianchiniite, Ba2(Ti4+V3+)(As2O5)2OF, has been discovered in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. It occurs as brown {001} tabular crystals, up to 1 mm across, with a vitreous lustre. It is brittle, with a perfect {001} cleavage. Streak is brownish. In reflected light, bianchiniite is grey, with orange–yellow internal reflections. It is weakly bireflectant, with a very weak anisotropy in shades of grey. Minimum and maximum reflectance data for COM wavelengths [Rmin/Rmax (%), (λ, nm)] are: 5.0/5.8 (470), 5.7/6.5 (546), 5.7/7.0 (589) and 5.2/6.3 (650). Electron microprobe analyses gave (wt.% – average of 10 spot analyses): TiO2 10.34, V2O3 3.77, Fe2O3 3.76, As2O3 44.36, Sb2O3 0.22, SrO 0.45, BaO 34.79, PbO 0.28, F 1.77, sum 99.74, –O = F –0.75, total 98.99. On the basis of 12 anions per formula unit, the empirical formula of bianchiniite is (Ba2.00Sr0.04Pb0.02)Σ2.06(Ti4+1.14V3+0.44Fe3+0.42)Σ2.00[(As3.96Sb0.02)Σ3.98O10](O1.18F0.82)Σ2.00. Bianchiniite is tetragonal, space group I4/mcm, with unit-cell parameters a = 8.7266(4), c = 15.6777(7) Å, V = 1193.91(12) Å3 and Z = 8. Its crystal structure was refined from single-crystal X-ray diffraction data to R1 = 0.0134 on the basis of 555 unique reflections with Fo > 4σ(Fo) and 34 refined parameters. The crystal structure shows columns of corner-sharing [Ti/(V,Fe)]-centred octahedra running along c, connected along a and b through (As2O5) dimers. A {001} layer of Ba-centred [10+2]-coordinated polyhedra is intercalated between (As2O5) dimers. Bianchiniite has structural relations with fresnoite- and melilite-group minerals. The name honours the two mineral collectors Andrea Bianchini (b. 1959) and Mario Bianchini (b. 1962) for their contribution to the knowledge of the mineralogy of pyrite ± baryte ± iron-oxide ore deposits from the Apuan Alps.

New occurrences of derbylite, Fex2+Fe3+4–2xTi4+3+xSb3+O13(OH), and graeserite, Fex2+Fe3+4–2xTi4+3+xAs3+O13(OH), have been identified in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. Derbylite occurs as prismatic to acicular black crystals in carbonate veins. Iron and Ti are replaced by V (up to 0.29 atoms per formula unit, apfu) and minor Cr (up to 0.04 apfu). Mössbauer spectroscopy confirmed the occurrence of Fe2+ (up to 0.73 apfu), along with Fe3+. The Sb/(As+Sb) atomic ratio ranges between 0.73 and 0.82. Minor Ba and Pb (up to 0.04 apfu) substitute. Derbylite is monoclinic, space group P21/m, with unit-cell parameters a = 7.1690(3), b = 14.3515(7), c = 4.9867(2) Å, β = 104.820(3)° and V = 495.99(4) Å3. The crystal structure was refined to R1 = 0.0352 for 1955 reflections with Fo > 4σ(Fo). Graeserite occurs as prismatic to tabular black crystals, usually twinned, in carbonate veins or as porphyroblasts in schist. Graeserite in the first kind of assemblage is V rich (up to 0.66 apfu), and V poor in the second kind (0.03 apfu). Along with minor Cr (up to 0.06 apfu), this element replaces Fe and Ti. The occurrence of Fe2+ (up to 0.68 apfu) is confirmed by Mössbauer spectroscopy. Arsenic is dominant over Sb and detectable amounts of Ba and Pb have been measured (up to 0.27 apfu). Graeserite is monoclinic, space group C2/m, with unit-cell parameters for two samples: a = 5.0225(7), b = 14.3114(18), c = 7.1743(9) Å, β = 104.878(3)°, V = 498.39(11) Å3; and a = 5.0275(4), b = 14.2668(11), c = 7.1663(5) Å, β = 105.123(4)° and V = 496.21(7) Å3. The crystal structures were refined to R1 = 0.0399 and 0.0237 for 428 and 1081 reflections with Fo > 4σ(Fo), respectively. Derbylite and graeserite are homeotypic. They share the same tunnel structure, characterised by an octahedral framework and cuboctahedral cavities, hosting (As/Sb)O3 groups and (Ba/Pb) atoms.

Alstonite, BaCa(CO3)2, is a mineral described almost two centuries ago. It is widespread in Nature and forms magnificent cm-sized crystals. Notwithstanding, its crystal structure was still unknown. Here, we report the crystal-structure determination of the mineral and discuss it in relationship to other polymorphs of BaCa(CO3)2. Alstonite is trigonal, space group P31m, with unit-cell parameters a = 17.4360(6), c = 6.1295(2) Å, V = 1613.80(9) Å3 and Z = 12. The crystal structure was solved and refined to R1 = 0.0727 on the basis of 4515 reflections with Fo > 4σ(Fo) and 195 refined parameters. Alstonite is formed by the alternation, along c, of Ba-dominant and Ca-dominant layers, separated by CO3 groups parallel to {0001}. The main take-home message is to show that not all structure determinations of minerals/compounds can be solved routinely. Some crystals, even large ones displaying excellent diffraction quality, can be twinned in complex ways, thus making their study a crystallographic challenge.

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.

The new mineral isselite, Cu6(SO4)(OH)10(H2O)4⋅H2O, has been discovered in the Lagoscuro mine, Monte Ramazzo mining complex, Genoa, Eastern Liguria, Italy. It occurs as sprays of blue acicular crystals, up to 0.1 mm long, associated with brochantite and posnjakite. Streak is light blue and the lustre is vitreous. Isselite is brittle, with irregular fracture and good cleavage on {001} and {100}. Measured density is 3.00(2) g/cm3. Isselite is optically biaxial (–), with α = 1.599(2), β = 1.633(2) and γ = 1.647(2) (determined in white light). The measured 2V is 63.6(5)°. Dispersion is moderate, with r > v. The optical orientation is X = b, Y = c and Z = a. Isselite is pleochroic, with X = light blue, Y = blue, Z = blue; X << Z < Y. Electron microprobe analyses give (wt.%): SO3 11.45(21), MgO 0.31(7), CoO 1.07(14), NiO 9.41(90), CuO 51.29(126), ZnO 1.10(20), H2Ocalc 24.21, total 98.84. The empirical formula of isselite, based on Σ(Mg,Co,Ni,Cu,Zn) = 6 atoms per formula unit, is (Cu4.80Ni0.94Co0.11Zn0.10Mg0.06)Σ6.00(S1.06O4.19)(OH)10⋅5H2O. Isselite is orthorhombic, space group Pmn21, with unit-cell parameters a = 6.8070(14), b = 5.8970(12), c = 20.653(4) Å, V = 829.0(3) Å3 and Z = 2. The crystal structure of isselite was refined from single-crystal X-ray diffraction data to R1 = 0.067 on the basis of 2964 reflections with Fo > 4σ(Fo). It shows a layered structure formed by zig-zag {001} layers of Cu-centred polyhedra. Sulfate groups occur in the interlayer along with one H2O group. Isselite is chemically related to redgillite and montetrisaite.

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.