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Three new members of the hakite series, Cu6(Cu4Me2+2)Sb4Se13; hakite-(Cd), hakite-(Fe) and hakite-(Zn) from the Bytíz deposit, uranium and base-metal Príbram ore district, Czech Republic
Hakite-(Cd), hakite-(Fe) and hakite-(Zn) are new minerals belonging to the tetrahedrite group and forming, along with hakite-(Hg), the hakite series. They have been discovered in samples collected from the Bytíz deposit, in the uranium and base-metal Príbram ore district, Central Bohemia, Czech Republic. They occur as anhedral grains, up to 300 µm in size, in a calcite gangue, associated with clausthalite, cadmoselite, hakite-(Hg) [for hakite-(Cd)], berzelianite, bukovite, bytízite, crookesite, chaméanite, eskebornite, príbramite, the not yet approved giraudite-(Hg) and giraudite-(Cu), hakite-(Hg), umangite, chalcopyrite, tetrahedrite-(Zn) and a new Cu-As selenide [for hakite-(Fe) and -(Zn)]. The three new species are black, with a metallic lustre. Mohs hardness is ca. 3 1/2-4; calculated density is 6.019 (Hak-Cd), 6.011 (Hak-Fe) and 6.081 g·cm-3 (Hak-Zn). In reflected light, they are isotropic, pale grey with bluish (Hak-Cd) or brownish (Hak-Fe and Hak-Zn) shades. Empirical formulae of hakite-(Cd), hakite-(Fe), and hakite-(Zn) are Cu9.71Ag0.24Cd1.51Hg0.43Zn0.03(Sb3.94As0.13)Σ4.07Se11.35S1.5 7, Cu10.11Ag0.18Fe0.81Zn0.50Hg0.26(Sb3.72As0.41)Σ4.13Se12.65S0. 12, and Cu10.03Ag0.24Zn0.61Fe0.53Hg0.45(Sb3.55As0.60)Σ4.15Se12.82S0. 08, respectively. These formulae correspond to the end-member formulae Cu6(Cu4Cd2)Sb4Se13 (Hak-Cd), Cu6(Cu4Fe2)Sb4Se13 (Hak-Fe), and Cu6(Cu4Zn2)Sb4Se13 (Hak-Zn). All these new members of the hakite series are cubic, I4̄3m, Z = 2, with unit-cell parameters a = 10.8860(6) Å, V = 1290.0(2) Å3 (Hak-Cd); a = 10.7983(4) Å, V = 1259.12(14) Å3 (Hak-Fe); and a = 10.8116(14) Å, V = 1263.8(5) Å3 (Hak-Zn). These species are isotypic with the other members of the tetrahedrite group, and their crystal structures have been refined on the basis of single-crystal X-ray diffraction data down to R1 values of 0.0230 (Hak-Cd), 0.0254 (Hak-Fe), and 0.0302 (Hak-Zn). These structural data allow us to describe the S-to-Se partitioning in hakite-series minerals and to understand the mechanisms avoiding too short Me-Se distances in these selenides.
Journal Article
Theuerdankite, Ag3AsO4, a new mineral from the Alter Theuerdank Mine, St. Andreasberg, Germany
The new mineral theuerdankite, ideally Ag3AsO4, was found in the Alter Theuerdank Mine, Beerberg, St. Andreasberg, Goslar District, Lower Saxony, Germany. Theuerdankite occurs as aggregates of anhedral grains up to 3 mm in size, growing in cavities of strongly supergene-weathered material consisting of native silver and chlorargyrite (but with calcite present). It is dark violet, changing to reddish and black when exposed to the air and light. It has a grey to violet grey streak; when readily fresh, its streak is brownish-red. The Mohs hardness is ∼2. It is brittle with no observable cleavage or parting and with a conchoidal fracture. The calculated density is 6.620 g·cm-3. In reflected light, theuerdankite is dark grey with a pinkish tint, with no observable bireflectance, pleochroism, or anisotropy. It shows dark red internal reflections. The reflectance values for wavelengths recommended by the Commission on Ore Mineralogy of the International Mineralogical Association are (R, %): 13.3 (470 nm), 12.8 (546 nm), 12.7 (589 nm) and 12.5 (650 nm). The empirical formula (based on 4 apfu) is Ag3.00As1.00O4. Theuerdankite is cubic, space group P4̄3n, a = 6.144(2) Å, V = 231.93(13) Å3 and Z = 2. The six strongest powder X-ray diffraction lines are [dobs in Å, (I) hkl]: 3.0736, (22) 200; 2.7502, (100) 210; 2.5106, (55) 211; 1.7050, (36) 320; 1.6249, (44) 321; and 1.3412, (17) 421. The crystal structure of theuerdankite (R1 = 1.69% for 519 reflections having I > 3σ(I)), is isotypic to those of synthetic Ag3AsO4 and Ag3PO4. The Gram-Charlier development describing the higher-order tensors representing the atomic displacement parameters of the silver atom was implemented, documenting that silver tends to behave anharmonically in the theuerdankite structure at room temperature.
Journal Article
Markwelchite, TlPbSbS3, a new Tl-Pb sulfosalt from the hydrothermal deposit of Jas Roux, Hautes-Alpes, France
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)(2̄11); 3.78 (90)(210); 3.29 (90)(102); 2.73 (85)(1̄13); 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.
Journal Article
Sperlingite, (H2O)K(Mn2+Fe3+)(Al2Ti)(PO4)4O(OH)(H2O) 9(OH)·4H2O, a new paulkerrite-group mineral, from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria, Germany
Sperlingite, (H2O)K(Mn2+Fe3+)(Al2Ti)(PO4)4[O(OH)][(H2O)9(OH)]·4H2 O, is a new monoclinic member of the paulkerrite group, from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria, Germany. It was found in corrosion pits of altered zwieselite, in association with columbite, hopeite, leucophosphite, mitridatite, scholzite, orange-brown zincoberaunite sprays and tiny green crystals of zincolibethenite. Sperlingite forms colourless prisms with pyramidal terminations, which are predominantly only 5 to 20 µm in size, rarely to 60 µm and frequently are multiply intergrown and are overgrown with smaller crystals. The crystals are flattened on {010} and slightly elongated along [100] with forms {010}, {001} and {111}. Twinning occurs by rotation about c. The calculated density is 2.40 g·cm-3. Optically, sperlingite crystals are biaxial (+), α = 1.600(est), β = 1.615(5), γ = 1.635(5) (white light) and 2V (calc.) = 82.7°. The optical orientation is X = b, Y = c and Z = a. Neither dispersion nor pleochroism were observed. The empirical formula from electron microprobe analyses and structure refinement is A1[(H2O)0.96K0.04]Σ1.00A2(K0.52∎0.48)Σ1.00M1(Mn 2+0.60Mg 0.33Zn0.29Fe3+0.77)Σ1.99M2+M3(Al1.05Ti4+1.33Fe3+ 0.62)Σ3.00 (PO4)4X[F0.19(OH)0.94O0.87]Σ2.00[(H2O)9.23(OH)0.77 ]Σ10.00·3 .96H2O. Sperlingite has monoclinic symmetry with space group P21/c and unit-cell parameters a = 10.428(2) Å, b = 20.281(4) Å, c = 12.223(2) Å, β = 90.10(3)°, V = 2585.0(8) Å3 and Z = 4. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.058 for 5608 reflections with I > 3σ(I). Sperlingite is the first paulkerrite-group mineral to have co-dominant divalent and trivalent cations at the M1 sites; All other reported members have Mn2+ or Mg dominant at M1. Local charge balance for Fe3+ at M1 is achieved by H2O → OH- at H2O coordinated to M1.
Journal Article
Xenotime-(Gd), a new Gd-dominant mineral of the xenotime group from the Zimna Voda REE-U-Au quartz vein, Prakovce, Western Carpathians, Slovakia
Xenotime-(Gd), ideally GdPO4, is a new mineral of the xenotime group. It was discovered at the Zimná Voda REE-U-Au occurrence near Prakovce, Western Carpathians, Slovakia. It forms rare crystal domains (≤20 µm, usually ≤10 µm in size) in Gd-rich xenotime-(Y) crystals (≤100 µm in size), in association with monazite-group minerals, uraninite, fluorapatite and uranyl arsenates-phosphates. The hydrothermal REE-U-Au mineralisation occurs in a quartz-muscovite vein, hosted in Palaeozoic phyllites near exocontact with Permian granites. The density is 5.26 g/cm3, based on calculated average empirical formula and unit-cell parameters. The average chemical composition (n = 6) measured by electron microprobe is as follows (wt.%): P2O5 30.1, As2O5 0.5, SiO2 0.2, UO2 0.3, Y2O3 15.7, (La, Ce, Pr, Nd)2O3 0.5, Sm2O3 5.7, Eu2O3 1.4, Gd2O3 29.2, Tb2O3 3.9, Dy2O3 10.4, Ho2O3 0.4, (Er, Tm, Yb, Lu)2O3 2.1, (Ca, Fe, Pb, Mn, Ba)O 0.1, total 100.5. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.37Y0.32Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Tm0.01Nd0.01...)Σ1 .01(P0.98As0.01Si0.01)O4. The empirical formula of the Gd-richest composition is: (Gd0.38Y0.31Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Nd0.01Ho0.01...)Σ1 .01(P0.98As0.01Si0.01)O4. The ideal formula is GdPO4. The xenotime-type structure has been confirmed by micro-Raman spectroscopy and a Fast Fourier-Transform pattern using HRTEM. Xenotime-(Gd) is tetragonal, space group I41/amd, a = 6.9589(5) Å, c = 6.0518(6) Å, V = 293.07(3) Å3 and Z = 4. The new mineral is named as an analogue of xenotime-(Y) and xenotime-(Yb) with Gd dominant among the REE. The middle REE enrichment of xenotime-(Gd) is shared with the associated monazite-(Gd) and Gd-rich hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing minerals is a product of selective complexing and enrichment in MREE in low-temperature hydrothermal fluids by alteration of uraninite, brannerite and fluorapatite on a micro-scale. The existence of xenotime-(Gd) and monazite-(Gd) is the first naturally documented dimorphism among REE phosphates. In addition, xenotime-(Gd) is only the third approved Gd-dominant mineral, after lepersonnite-(Gd) and monazite-(Gd).
Journal Article
Ferriphoxite and carboferriphoxite; two new oxalato-phosphate minerals from the Rowley Mine, Arizona, USA
Ferriphoxite, [(NH4)2K(H2O)][Fe3+(HPO4)2(C2O4)], and carboferriphoxite, [(NH4)K(H2CO3)][Fe3+(HPO4)(H2PO4)(C2O4)], are new mineral species from the Rowley mine, Maricopa County, Arizona, USA. They occur with antipinite, aphthitalite, baryte, fluorite, hematite and quartz in an unusual bat-guano-related, post-mining assemblage. Ferriphoxite occurs as rectangular blades, up to ∼0.1 mm in length, typically forming sprays. Carboferriphoxite occurs as needles or blades, up to ∼0.2 mm in length, typically forming fan- and bowtie-like sprays. Both species are colourless with white streak, vitreous lustre, ∼2 Mohs hardness, brittle tenacity and splintery fracture. Ferriphoxite has three good cleavages ({100}, {010} and {001}) and carboferriphoxite has two good cleavages (probably {100} and {001}). Both species have a measured density of 2.14(2) g·cm-3. Ferriphoxite is biaxial (+) with α = 1.524(3), β = 1.560(3), γ = 1.608(3) and 2Vmeas. = 83.9(4)°. Carboferriphoxite is biaxial (+) with α = 1.525(3), β = 1.555(calc), γ = 1.630(3) and 2Vmeas. = 67(1)°. Electron probe microanalysis gave {[(NH4)2.13K0.87]Σ3.00(H2O)} {(Fe3+0.95Al0.05)Σ1.00(HPO4)2(C2O4)} for ferriphoxite and {[(NH4)1.12K0.88]Σ2.00(H2CO3)} {(Fe3+0.78Al0.22)Σ1.00(HPO4)(H2PO4)(C2O4)} for carboferriphoxite. Ferriphoxite is monoclinic, P21/c, with a = 11.389(5), b = 6.352(3), c = 18.716(9), β = 102.887(9)°, V = 1319.8(11) Å3 and Z = 4. Carboferriphoxite is triclinic, P1̄, with a = 6.4405(3), b = 9.399(5), c = 11.839(6) Å, α = 95.763(10), β = 92.314(10), γ = 100.665(8)°, V = 695.6(6) Å3 and Z = 2. The structures of ferriphoxite (R1 = 0.0678 for 1850 I > 2σI reflections) and carboferriphoxite (R1 = 0.0427 for 3602 I > 2σI reflections) both contain double-strand chains of corner-sharing Fe3+O6 octahedra and PO3(OH) tetrahedra. The chain in ferriphoxite is decorated by PO3OH tetrahedra and C2O4 groups and that in carboferriphoxite is decorated by PO2(OH)2 tetrahedra and C2O4 groups. The interstitial units in both structures contain K+ and NH4+ cations along with a H2O group in ferriphoxite and an H2CO3 group in carboferriphoxite.
Journal Article
Ferriandrosite-(Ce), a new member of the epidote supergroup from Betliar, Slovakia
A new member of the epidote supergroup, ferriandrosite-(Ce), ideally MnCeFe3+AlMn2+(Si2O7)(SiO4)O(OH), was found at the Július manganese ore occurrence near Betliar, Rožňava Co., Kosice Region, Slovakia. It occurs as subhedral grains and polycrystalline aggregates, up to 0.3 mm in size, enclosed in pyroxmangite. Other associated minerals are spessartine, rhodochrosite, quartz, baryte and pyrosmalite-(Mn). Ferriandrosite-(Ce) is dark brown, with a light brown streak and vitreous lustre. The Mohs hardness is ∼6 1/2 to 7 and tenacity is brittle with no observable cleavage or fracture. The calculated density is 4.321 g·cm-3. Ferriandrosite-(Ce) is optically biaxial (+), with weak pleochroism, high surface relief and the mean calculated refractive index is 1.832. The empirical structural formula of ferriandrosite-(Ce), based on 13 anions per formula unit, is A1(Mn2+0.63Ca0.35Ce0.02)Σ1.00A2(Ce0.53La0.27Nd0.14Pr0.05REE *0.01)Σ1.00M1(Fe3+0.41Al0.12V3+0.01Mg0.40Ti0.05)Σ0.99M2Al 1.00M3(Mn2+0.75Fe2+0.22Mg0.03)Σ1.00T1-3Si3.00O11O4(O0.67F0.33) (OH), where REE* are minor rare earth elements. Ferriandrosite-(Ce) is monoclinic, space group P21/m, a = 8.8483(4) Å, b = 5.7307(3) Å, c = 10.0314(5) Å, β = 113.3659(15)°, V = 466.95(4) Å3 and Z = 2. The crystal structure of ferriandrosite-(Ce) was refined to a final R1 = 0.0210 for 1910 reflections with Fo > 4σ(Fo) and 127 refined parameters. Structural features of ferriandrosite-(Ce) are discussed and compared with other members of the androsite-series.
Journal Article
Kvacekite, NiSbSe, a new selenide mineral from Bukov, Czech Republic
Kvacekite is a new mineral species discovered in a sample collected from the now abandoned Bukov uranium mine, western Moravia, Czech Republic. It occurs as rare anhedral grains, up to 15 µm in size, associated with nickeltyrrellite, tyrrellite, berzelianite, hakite-(Zn), hakite-(Cd), eucairite, clausthalite, and gold in calcite gangue. In reflected light, kvacekite is white with a faint yellowish shade; bireflectance, pleochroism and anisotropy are absent. Internal reflections were not observed. Reflectance values for the four COM wavelengths for kvacekite in air [R (%) (λ in nm)] are: 54.9 (470); 53.5 (546); 52.6 (589); and 52.2 (650). The empirical formula, based on electron-microprobe analyses (EPMA), is (Ni0.95Cu0.04Co0.03)Σ1.02Sb1.00(Se0.97S0.01)Σ0.98. The ideal formula is NiSbSe, which requires (in wt.%) Ni 22.63, Sb 46.93, Se 30.44, total 100.00. Kvacekite is cubic, P213, with unit-cell parameters a = 6.09013(13) Å, V = 225.881(15) Å3 and Z = 4. The strongest reflections in the X-ray powder diffraction pattern of synthetic kvacekite [d, Å (I) hkl] are: 3.0458 (11) 200; 2.7242 (100) 201, 210; 2.4867 (71) 211; 1.8632(39) 311; 1.6277(29) 321, 312; and 1.3290 (13) 421. Given the similarity with ullmannite, NiSbS, the crystal structure was refined from the powder X-ray diffraction data starting from those atomic coordinates using the synthetic analogue of kvacekite. Its crystal structure is formed by corner-sharing [NiSb3Se3] octahedra which form a three-dimensional network. The identity of the natural kvacekite and synthetic cubic NiSbSe were confirmed by a study of their chemical composition, reflectance measurements, Raman spectroscopy and electron back-scattered diffraction (EBSD) measurements on the mineral. Kvacekite is named after Milan Kvacek (1930-1993), a prominent Czech mineralogist. The mineral and its name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2023-095).
Journal Article
Manganonewberyite, Mn(PO3OH)(H2O)3, the manganese analogue of newberyite from the Cassagna Mine, Italy
The new mineral manganonewberyite (IMA2024-004), Mn(PO3OH)(H2O)3, was found underground at the Cassagna mine, Liguria, Italy, where it is a secondary phase formed by the interaction of bat guano with Mn-rich rock. Manganonewberyite occurs with niahite, kutnohorite, sampleite and serrabrancaite on a tinzenite-quartz-braunite matrix. Crystals are prisms and blades, up to ∼0.15 mm long, elongated parallel to [001], flattened on {100} and exhibiting the forms {100}, {010} and {111}. Crystals are colourless and transparent, with vitreous lustre and white streak. The mineral is brittle with curved fracture. The Mohs hardness is ∼3. Cleavage is perfect on {010}. The density is 2.34(2) g·cm-3. Optically, manganonewberyite is biaxial (+) with α = 1.541(2), β = 1.547(2) and γ = 1.559(2) (white light). The 2V is 71.6(3)°. The optical orientation is X = a, Y = b and Z = c. The empirical formula is (Mn0.960Mg0.016Ca0.015)Σ0.991(H1.02P1.00O4)(H2O)3. Manganonewberyite is orthorhombic, space group Pbca, with cell parameters: a = 10.4273(6), b = 10.8755(8), c = 10.2126(4) Å, V = 1158.13(11) Å3 and Z = 8. The crystal structure (R1 = 2.79% for 892 I > 2σI reflections) is the same as that of newberyite with Mn in place of Mg.
Journal Article