The new mineral polyarsite, ideally Na7CaMgCu2(AsO4)(4)F2Cl, was discovered in high-temperature incrustations of the active Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with aegirine, sanidine, ferrisanidine, hematite, halite, sylvite, cassiterite, evseevite, axelite, badalovite, johillerite, arsmirandite, aphthitalite, tridymite, potassic-magnesio-fluoro-arfvedsonite and litidionite. Polyarsite forms short-prismatic, equant or tabular crystals up to 0.15 mm across, their clusters up to 0.3 mm in size or crusts up to 0.5 mm across and up to 0.03 mm thick. Polyarsite is transparent, sky-blue to light blue, with vitreous lustre. It is brittle, no cleavage is observed and the fracture is uneven. Dcalc. = 3.592 g cm-3. Polyarsite is optically biaxial (+), alpha = 1.624 (4), beta = 1.645 (4), gamma = 1.682 (4) (589 nm), 2V(meas.) = 70 (10)degrees. The empirical chemical formula calculated based on 19 O+F+Cl apfu is Na7.04Ca1.00Mg0.92Cu2.06Fe0.063+(As3.96S0.05)(Sigma 4.01)O16.28F1.66Cl1.06. Polyarsite is monoclinic, space group I2/m, a = 8.4323(4), b = 10.0974(4), c = 10.7099(6) angstrom, beta = 90.822(4)degrees, V = 911.79(8) angstrom(3) and Z = 2. The crystal structure was determined based on SCXRD data, R = 0.0391. Polyarsite demonstrates a novel structure type. The structure is based on the (1 0 1) heteropolyhedral layers formed by Cu2O8Cl dimers built by CuO4Cl tetragonal pyramids sharing common Cl vertex, AsO4 tetrahedra and MgO4F2 octahedra. Adjacent layers are linked via CaO8 cubes to form a pseudo-framework which hosts octahedrally coordinated Na cations. Polyarsite was named based on the Greek words pi omicron lambda upsilon sigma, poly, "many" and due to belonging to arsenates: this arsenate contains many chemical components ordered between different positions in crystal structure.

The new mineral magganasite, ideally CuFe3+3O(AsO4)3, was found in the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with sanidine, lammerite, paralammerite, johillerite, calciojohillerite, alarsite, hematite, tenorite, cassiterite, langbeinite, euchlorine, fedotovite and wulffite. Magganasite forms prismatic crystals up to 0.2 mm long and up to 0.04 mm thick typically assembled in clusters up to 1 mm across. It is translucent, golden- or red-brown to brownish-yellow, with strong vitreous to semi-metallic lustre. Dcalc is 4.708 g cm-3. In reflected light, magganasite is grey, weakly anisotropic. The reflectance values [Rmax-Rmin,% (lambda, nm)] are: 13.1-13.1 (470), 12.5-11.9 (546), 12.2-11.9 (589), 11.9-11.8 (650). Chemical composition (wt.%, electron microprobe data) is: CuO 14.69, ZnO 0.06, Al2O3 0.49, Cr2O3 0.19, Fe2O3 30.62, TiO2 2.22, SiO2 0.21, P2O5 0.12, V2O5 0.10, As2O5 50.72, SO3 0.63, total 100.05. The empirical formula based on 13 O apfu is Cu1.22Al0.06Cr0.02Fe3+2.52Ti0.18(As2.91S0.05Si0.02P0.01V0.01)Sigma 3.00O13. Magganasite is triclinic, P $\bar 1$, a = 5.1813(7), b = 9.6427(11), c = 9.6834(11) & Aring;, alpha = 82.066(10), beta = 78.680(11), gamma = 79.962(10)degrees, V = 464.41(10) & Aring;3 and Z = 2. The strongest reflections of the PXRD pattern [d,& Aring;(I)(hkl)] are: 3.761(100)(102, 120), 3.540(46)(022), 3.280(88)(1 $\bar 1$2), 3.204(62)( $\bar 1$20), 3.170(41)( $\bar 1$02, 030), 2.989(51)( $\bar 1$12), 2.889(65)(103, 130), and 2.510(64)(200). The crystal structure, solved from single-crystal XRD data (R = 0.0609), is unique. It is based on the polyhedral ribbons built by two zig-zag chains of edge-sharing Fe2- and Fe3-centred octahedra linked via dimers of edge-sharing Cu-centred distorted tetragonal pyramids. The neighbouring ribbons are linked via dimers of edge-sharing Fe1-centred octahedra. AsO4 tetrahedra reinforce the linkage between the ribbons. The mineral is named in honour of the Greek mineralogist and petrologist Prof. Dr. Andreas Magganas (born 1954).

In most cases, columbite-supergroup minerals are characterized by partial ordering of cations, which makes their identification based only on chemical composition and powder diffraction data difficult. Columbite-supergroup minerals with partially ordered cations were studied by means of electron microprobe analyses, powder and single-crystal X-ray diffraction, including crystal structure refinement in ixiolite-type and wolframine-type models. The samples originate from the Sakhanaiskiy granite massif, Eastern Siberia, Russia, (Sample 1) and from the Heftetjern pegmatite, Telemark, Norway (Sample 2). Their representative empirical formulae are (Fe2+0.81Mn2+0.53)Sigma 1.34Fe3+0.07(Ti0.23Zr0.11Sn0.02)Sigma 0.36(Nb1.45Ta0.26)Sigma 1.71W0.52O8 (Sample 1) and (Mn2+0.28Fe2+0.25)Sigma 0.53Sc1.08(Sn0.32Ti0.04)Sigma 0.36(Ta1.41Nb0.52)Sigma 1.93W0.10O8 (Sample 2). Based on these data and the results of the crystal structure refinement, the studied samples can be considered as columbite-supergroup minerals in which cations are partially ordered in accordance with the wolframite mechanism. An approach is suggested according to which the degree of cation ordering in such columbite-supergroup minerals can be estimated based on the electron contents refined for different sites in a monoclinic model. According to this criterion, the degree of cation ordering of Samples 1 and 2 is 91% and 26%, respectively. Despite a significant degree of cation disordering, transition from the wolframite to ixiolite model results in a significant enhancement of the R-factor of the structure refinement (from 0.0365 to 0.0764 and from 0.0207 to 0.0610, respectively).

The new alluaudite-group mineral manganobadalovite (IMA 2020-035), ideally NaNaMn(MgFe3+)(AsO4)3, was found in the Arsenatnaya fumarole, the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption 1975-1976, Tolbachik volcano, Kamchatka peninsula, Far-Eastern Region, Russia. Manganobadalovite is a fumarolic mineral, and its aggregates are found overgrowing basalt scoria or exhalative hematite crystal crusts. Associated minerals are badalovite, hematite, cassiterite, sanidine, glauberite and metath & eacute;nardite. Manganobadalovite occurs as prismatic to equant crystals up to 0.8 mm long typically combined in open-work clusters; it also forms grains that are irregular in shape and cavernous granular crusts up to 0.5 cm. The mineral is transparent, with vitreous luster, and its color varies from red to yellow. Manganobadalovite is brittle and has a noticeable cleavage in one direction and uneven fracture. The calculated density is 4.108 g cm-3. Manganobadalovite is optically biaxial (+), alpha = 1.790 (7), beta = 1.800 (7), gamma = 1.815 (8) and 2Vmeas = 80 (5)degrees. Chemical composition (wt.%, electron-microprobe): Na2O 8.75, K2O 0.17, MgO 5.32, CaO 3.68, MnO 10.09, CuO 0.42, Al2O3 0.18, Fe2O3 13.90, V2O5 0.42, As2O5 56.75, total 99.68. The empirical formula calculated based on 12 O apfu is Na1.69K0.02Ca0.39Mn0.85Mg0.79Cu0.03Fe3+1.04Al0.02(As2.96V0.03)& sum;2.99O12. The crystal structure was solved using single-crystal XRD data, R = 2.30%. Manganobadalovite is monoclinic, C2/c, a = 12.1848(5), b = 12.8924(4), c = 6.6970(3) & Aring;, beta = 113.113(5)degrees, V = 967.60(7) & Aring;3 and Z = 4. The strongest reflections of the powder XRD pattern are [d,& Aring;(I)(hkl)]: 6.43(30)020, 3.589(32)(-131, 310), 3.215(38)(040, -112), 3.079(23)(221, 002), 2.941(32)(-312, -222, -331), 2.852(15)(041), 2.788(100)(330, 400, 240, 022), 2.649(22)(-402, 112), 2.626(25)(-132). Manganobadalovite is named as an analogue of badalovite NaNaMg(MgFe3+)(AsO4)3 with Mn2+ prevailing in the M(1) site.

A nearly continuous series of metacinnabar-sphalerite solid solutions is reported in assemblages of Zn-rich metacinnabar in gold-bearing carbonate breccias of the Vorontsovskoe gold deposit, Northern Urals, Russia. Metacinnabar occurs as grains containing paragenetic inclusions of realgar, specific thallium-bearing sulfosalts, high-fineness native gold, and various ZnS-HgS minerals, including Zn-bearing metacinnabar, Hg-bearing sphalerite, and pure cinnabar. Selected metacinnabar-sphalerite compositions fall within the (Hg0.54Zn0.46)S-(Zn0.62Hg0.38)S range. This finding confirms the absence of the long-debated miscibility gap (MG), which was previously constrained to (Hg0.54Zn0.46) S-(Zn0.75Hg0.25)S in the natural HgS-ZnS cubic system. The compositions obtained within the MG have the following major components ranges (wt%): Zn (17.7-27.3), Hg (50.7-63.6), and S (18.7-22.0). Compositional zoning in Zn and Hg contents is observed in metacinnabar. The core consists of either highly Hg-enriched sphalerite or Zn-enriched metacinnabar, while the rim is composed of low-Zn metacinnabar (3-5 wt% Zn). The Hg/Zn ratio gradually increases from core to periphery. Metacinnabar also contains minor impurities of Mn (up to 1.2 wt%) and Cd (up to 2.6 wt%). Mn is a nearly constant constituent. Based on published compositional data on sphalerite-metacinnabar from 38 localities, Mn is considered an indicator for these minerals in Vorontsovskoe. Zoned Zn- and Mn-bearing metacinnabar formed during cooling (from <350 degrees C to <200 degrees C) of late-stage hydrothermal fluids enriched in chalcophile Tl-Cu-Zn-Hg-As-Sb-S elements. Our study suggests that a complete series of ZnS-HgS solid solutions may be found in hydrothermal systems with a relatively high-temperature formation regime (>250 degrees C). In addition, Zn-Mn-bearing metacinnabar is a metastable phase in the Zn-Hg-Mn-S system. Mn is considered a stabilizer for metacinnabar, a natural counterpart of beta-HgS, which is a prospective zero-gap semiconductor.

The enigma of ammonium mineral speciation in the solar system has no proven solution due to the lack of data on the real minerals serving as space ammonium carriers. We herein report on the discovery of the first ammonium mineral in meteoritic substance and show its relevance to compositional and spectral characteristics ascribed to hypothetical ammonium phases in cometary and asteroidal bodies. Chemically distant from previously inferred volatile organics or ammoniated phyllosilicates, the mineral is an aqueous metal-ammonium sulfate related to the picromerite group-a family of so-called Tutton's salts. Nickeloan boussingaultite, (NH4)2(Mg,Ni)(SO4)26H2O, was discovered in Orgueil, a primitive carbonaceous chondrite closely related to (162173) Ryugu and (101955) Bennu, the C-type asteroids. The available spectroscopic, chemical, and mineralogical data signify that natural sulfates related to boussingaultite-nickelboussingaultite series perfectly fit into the role of bound ammonia carriers under conditions of cometary nuclei and carbonaceous asteroids. The potential technogenic contamination of astromaterial samples and the difficulties in electron microprobe determination of ammonium are discussed in the context of recently published reports on the discovery of lunar and asteroidal ammonium-containing minerals.

Iron is one of the most common elements on Earth and is present in the modern crust mainly in the form of (hydro)oxides and silicates, whereas terrestrial (telluric) native Fe is extremely rare. It is generally assumed that telluric Fe differs greatly in its chemical composition and mineralogy from the metal of iron meteorites, indicating different modes of formation. We uncover haxonite (NiFe22C6) and uakitite (VN) within telluric iron assemblages in terrestrial crustal rocks (volcanic rocks of the Norilsk ore region, Russia and metamorphic rocks of the Hatrurim Basin, Israel, respectively). Both minerals were previously discovered in iron meteorites and were thought to be absent in Earth's crustal rocks. Consequently, we analyzed available data on terrestrial rocks containing native iron and iron meteorites and compared their oxygen-free mineral assemblages. The resemblance in mineralogy suggests that at least some metal-rich asteroids may have formed in a manner similar to telluric iron. We suggest that heating at low pressures (T approximate to 1000 degrees C, P < 10 MPa) of the primary Fe-bearing silicates in the presence of organic matter led to the formation of an iron melt at low oxygen fugacity (up to 5 units below Fe-FeO buffer). Significant differences in the geochemistry of terrestrial and extraterrestrial iron are associated with different degrees of evolution of the primary minerals involved in their formation.

Mampsisite is a new mineral in the hydrocalumite group-a family of natural layered double hydroxides (LDH), the analogs of cementitious calcium aluminates, or AFm phases. The mineral is the first purely carbonate member of the hydrocalumite group. Mampsisite was discovered in peralkaline hydrothermal assemblages confined to pyrometamorphic rocks of the Hatrurim Basin in the Negev Desert, near the Israeli coast of the Dead Sea. The mineral occurs in the cavities of marble-like larnite-brownmillerite-jasmundite rock, where it associates with katoite, portlandite, and other natural Ca-Al LDH: kuzelite Ca4Al2(OH)12(SO4)& centerdot;6H2O, hydrocalumite Ca4Al2(OH)12(Cl,CO3,OH)2 & centerdot;4H2O, and mariakrite Ca4Al2(OH)12(Fe2S4)& centerdot;4H2O. The assemblage was formed from residual highly alkaline solutions produced by late hydrothermal alteration of larnite, Ca2SiO4, and jasmundite, Ca11(SiO4)4 O2S. Mampsisite forms colorless platy crystals up to 50 mu m across with a perfect cleavage on {001}. Calculated density is 2.180 g & centerdot;cm-3. Chemical composition (electron microprobe, wt%, water, and CO2 calculated from structural data): CaO 39.12, Al2O3 17.66, CO2 7.66, H2O 34.49, total 98.93, corresponding to the empirical formula Ca4.01Al1.99(CO3)1.00(OH)11.99 & centerdot;5.00H2O or ideally Ca4Al2 (OH)12(CO3)& centerdot;5H2O. The mineral is triclinic, space group P1, a = 5.7834(2), b = 9.9274(3), c = 15.0972 (4) & Aring;, alpha = 87.198(2), beta = 89.805(2), gamma = 89.967(2)degrees, V = 865.75(5) & Aring;3, and Z = 2. The crystal structure (R1 = 0.053) represents an ordered 1:1 interstratification of two kinds of fully ordered layered units: the positively charged, carbonate-free hydrocalumite layer [Ca4Al2(OH)12(H2O)4]2+ and the negatively charged AFm layer of previously unknown type [Ca4Al2(OH)12(H2O)2(CO3)2]2-. The counter-charged layers are separated by two H2O molecules per formula unit, which are lying in the interlayer. This arrangement is different from that of synthetic AFm monocarboaluminate, which is composed of the uniform neutral units [Ca4Al2(OH)12(H2O)3(CO3)]0. However, both layer arrangements yield the same bulk chemical formula, Ca4Al2(OH)12(CO3)& centerdot;5H2O. The strongest lines of X-ray powder diffraction pattern of mampsisite [d in & Aring;(I)(hkl)]: 7.58(100)(002), 3.774(37)(004), 2.845(11)(131), 2.724(14)(132), 2.514(20)(203), 2.451(19)(133), 2.330(14)(134). It should be emphasized that basal interlayer spacing of mampsisite is almost identical to that of synthetic AFm monocarboaluminate and to basal spacings of 2:1 layered double hydroxides-quintinite, Mg4Al2(OH)12(CO3)& centerdot;3H2O, and the members of the quintinite group. The latter implies that mampsisite may be relatively common but a hidden constituent of cementitious materials and natural Ca-bearing clays, being readily misidentified with another polymorph of AFm monocarboaluminate and quintinite during the routine powder XRD analyses.

First-row transition metal (Me) phosphides are the cost-effective materials in sustainable chemistry, including applications in hydrogen evolution reaction and the development of alkaline-metal-ion batteries. However, thermal behavior and vibrational properties of transition metal phosphides have been poorly studied. We report data on Ni5P4, one of the technologically demanded nickel phosphides, which was investigated by means of scanning electron microscopy, electron microprobe analyses, electron backscatter diffraction, Raman spectroscopy combined with Density Functional Theory and single-crystal X-ray diffraction (over the temperature range of 163-773 K). For the first time we determine its thermal expansion coefficient (alpha(V) = 19 x 10(-6) K-1) based on single crystal data, and showed that the crystal structure of Ni5P4 undergoes maximum expansion perpendicular to the c axis, and minimum expansion along the c axis. Ni5P4 has clear Raman spectrum (18 peaks, the most intense and best resolved peaks are 143, 203, 238, 314, 414, 425 and 476 cm(-1)). Our results evidence that quasi-metallic transition metal phosphides having Me/P ratio >1 can produce the quality Raman spectra applicable for their characterization.

Petersite-(Y) is identified in cavities of oxidation zone of the Mednorudyanskoe deposit (Central Urals). It forms blue acicular hexagonal crystals up to 0.5 × 0.007 mm in size, which are typically assembled in radial aggregates, and is associated with malachite, chrysocolla, opal, and ranciéite. This is the first finding of a phosphate member of the mixite group in Russia. The chemical composition of the Mednorudyansky petersite-(Y) is as follows (microprobe data; H2O content is calculated by stoichiometry, wt

Abstract A series of high-entropy sodalite-and cancrinite-type feldspathoids with mixed Cl – , Br – , I – , S 4 , S 2 O 3 2– , Na + , K + and Ca 2+ extra-framework species were synthesized under soft hydrothermal conditions, in order to evaluate the influence of heteroatomic substitutions on luminescence properties and thermal stability of feldspathoids. It was found that relative stability of either cubic sodalite or the hexagonal cancrinite framework is strongly dependent on the type of anionic species. The partial substitution of (Na, K) for Ca, along with the mixed halogen occupancy, substantially improves the thermal stability of sodalites. Novel data on intrinsic luminescence attributed to recombination of electron and hole on halogen-metal complexes within cages is presented. The intrinsic luminescence bands span the entire visible region and depend on the geometry of the cages. The excitation of the luminescence occurs at ∼5 eV (250 nm).

The new mineral natromolybdite, ideally Na2MoO42H2O, was found in the Arsenatnaya fumarole, Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. The associated minerals are halite, sylvite, aphthitalite, belomarinaite, powellite, hematite, sanidine, tilasite, johillerite, bradaczekite, badalovite, arsmirandite, wrightite, arsenatrotitanite, dmisokolovite, litidionite, rutile and cristobalite. Natromolybdite occurs as rectangular, octagonal or rhomb-like lamellar to thin-tabular crystals up to 40 mu m across and up to 3 mu m thick, in near-parallel, pile-like or rose-like aggregates and crystal crusts up to 0.2 mm across. It is transparent and colourless, with vitreous lustre. Dcalc is 2.573 g/cm3. The synthetic analogue of natromolybdite is optically biaxial (+), alpha = 1.575(2), beta = 1.576(2), gamma = 1.598(3) and 2Vmeas = 20(10)degrees. The chemical composition (wt.%, electron microprobe, H2O is calculated by stoichiometry) is: Na2O 25.51, K2O 0.66, SO3 1.04, MoO3 58.21, H2Ocalc 15.05, total 100.47. The empirical formula, calculated based on O = 6 apfu, is (Na1.971K0.034)Sigma 2.005(Mo0.968S0.031)Sigma 0.999O42H2O. Natromolybdite is orthorhombic, space group Pbca, a = 8.483(1), b = 10.577(2), c = 13.842(2) & Aring;, V = 1242.0(2) & Aring;3 and Z = 8. The nine strongest reflections of the powder XRD pattern [d,& Aring;(I)(hkl)] are: 6.92(100)(002), 4.243(20)(200), 4.206(32)(022), 3.618(31)(202), 3.310(31)(220), 3.169(49)(131), 3.067(21)(114), 2.987(30)(222) and 2.681(15)(204, 311). Natromolybdite (IMA-accepted symbol Nmyb) is named for the chemical composition. It is a natural analogue of a well-studied synthetic sodium molybdate dihydrate.

The new mineral kantorite was found in the Arsenatnaya fumarole, Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. The associated minerals are aphthitalite, langbeinite, arcanite, krasheninnikovite, vanthoffite, kononovite, wulffite, halite, sylvite, flinteite, fluoborite, chubarovite, johillerite, urusovite, zincite, tenorite, pseudobrookite, hematite, sanidine and fluorophlogopite. Kantorite occurs as long-prismatic to acicular crystals up to 0.1 x 0.01 mm which form near-parallel and bush-like open-work clusters up to 0.2 mm across. It is transparent, colourless, with vitreous lustre. Dcalc is 2.498 g cm-3. Kantorite is optically biaxial (+), alpha = 1.447(2), beta = 1.449(2), gamma = 1.452(2) and 2Vcalc = 79 degrees. The chemical composition (wt.%, electron microprobe data) is: Na2O 9.80, K2O 27.17, Rb2O 0.12, MgO 12.02, CaO 0.09, SO3 47.46, F 5.68, Cl 0.11, -O=(F,Cl) 2.42, total 100.03. The empirical formula calculated based on (O+F+Cl) = 9 apfu is (K1.94Na0.06)Sigma 2.00(Na1.00Ca0.01)Sigma 1.01Mg1.00(SO4.01)1.99(F1.01Cl0.01)Sigma 1.02. The idealised formula is K2NaMg(SO4)2F. Kantorite is orthorhombic, Pna21, a = 6.9894(7), b = 7.1378(7), c = 17.925(2) & Aring;, V = 894.25(16) & Aring;3 and Z = 4. Strong reflections of the powder XRD pattern [d,& Aring;(I)(hkl)] are: 8.99(91)(002), 4.83(57)(111), 4.498(43)(004), 3.588(47)(020), 3.511(74)(200), 3.270(43)(202), 2.926(100)(115), 2.805(44)(024), 2.768(53)(204) and 2.510(55)(220). The crystal structure was solved from single-crystal XRD data, R1 = 0.031. The structure of kantorite is unique. It represents a quasi-framework in which the basic units are octahedra [MgO4F2]. They are linked via bridging F atoms to form infinite chains. These chains are encrusted by [SO4] tetrahedra and assembled into the quasi-framework by alkali cations. The sulfate-encrusted chains of octahedra [MgO4F2] are topologically identical in the structures of kantorite and krasheninnikovite KNa2CaMg(SO4)3F. The mineral is named in honour of the Russian mineralogist Boris Zinovievich Kantor (1930-2022).

Hanswilkeite, KFe3+S2, is a new potassium-rich natural sulfide discovered in the pyrometamorphic suite of the Hatrurim Formation, southern Negev Desert, Dead Sea basin, Israel. The mineral occurs in sulfide-calcite assemblages confined to black-colored calcite-spurrite marbles. It forms single-crystal grains up to 1 mm in size, isometric to lath-like, and often intergrown with a less-common rasvumite, KFe2S3. Associated minerals include srebrodolskite, tilleyite, fluormayenite, cuspidine, fluorapatite, old-hamite, pyrite, and andradite.Macroscopically, hanswilkeite has a deep-purple color, dull metallic luster, and brown-black streak. The Mohs hardness is 2. Moderate cleavage was observed along the c-axis. The calculated density is 2.654 gcm-(3). The Raman spectrum contains the following bands: 379, 357, 289, 236, 167, 131, and 124 cm(-1). In reflected light, the mineral has very strong pleochroism from yellow-pink to dark-gray. Anisotropy is very strong, Delta R-589 = 69%. Reflectance values for COM required wavelengths measured in air, R-max/R-min (lambda, nm) (%): 16.0/9.2 (470); 19.6/9.3 (546); 18.5/9.0 (589); 32.0/9.3 (650). Chemical composition (electron microprobe, average of 6 points, wt%): K 23.78, Ca 0.44, Fe 34.75, Mn 0.60, Zn 0.47, S 39.46, Total 99.5, which corresponds to empirical formula (K0.98Ca0.02)(1.00) (Fe1.00Mn0.02Zn0.01)(1.03)S-1.98 (Sigma = 4 apfu) or ideally KFe3+S2. Single-crystal X-ray diffraction shows that the mineral is monoclinic, space group C2/c (#15), with unit-cell parameters a = 7.0914(5), b = 11.3154(5), c = 5.3992(3) & Aring;, beta = 113.244(7)degrees, V = 398.08(4) & Aring;(3), and Z = 4. Strongest lines of X-ray powder diffraction pattern [d in & Aring;(I)(hkl)]: 5.68(100)(020,110); 3.270(31)(130); 3.227(29)(111); 2.921(45)(221); 2.510(12)(131); 2.198(12)(132); 1.880(10)(330). The crystal structure has been solved and refined to R-1 = 0.038 for 454 unique observed reflections [I >= 2 sigma(I)]. The structure consists of infinite chains of edge-sharing tetrahedra [FeS4](-) centered with Fe3+; the sulfide chains are linked by K+ ions. Hanswilkeite is the third discovered dithioferrate mineral: a sulfosalt that contains [FeS2](-) anion with iron in Fe3+ state. Other known natural dithioferrates are erdite, NaFeS22H(2)O, and raguinite, TlFeS2. Hanswilkeite has a synthetic counterpart and a group of related synthetic sulfides and selenides, which were well studied due to specific electrical and magnetic properties owed to their quasi-one-dimensional structures. The mineral can be considered as an indicator of an extreme potassium-rich environment superimposed onto anhydrous and oxidizing formation conditions. The association with oldhamite is herein discussed in view of super-reduced conditions previously supposed for oldhamite geosynthesis.

The sulfide-free metasomatic rocks with chalcophile metals from the Ne & zcaron;ilovo ore field, near Veles, Republic of North Macedonia belong to a rare kind of ore. The mineralogy and petrology of these rocks were studied in detail and can be considered as a standard description for ores of this type. A characteristic feature of Ne & zcaron;ilovo-type ores is a wide variety of accessory oxide minerals containing chalcophile elements (Zn, Pb, Sb, Cu and As). The new nolanite-supergroup mineral zincorinmanite-(Zn), ideally (Fe3+2Zn)SbZnO7(OH), was discovered in the Ne & zcaron;ilovo ore. The associated minerals are quartz, baryte, gahnite, Zn-bearing phlogopite, together with accessory hematite, almeidaite, a Pb-analogue of hydroxycalciorom & eacute;ite and an insufficiently studied Sb-rich h & ouml;gbomite-supergroup mineral. Zincorinmanite-(Zn) forms lamellar to tabular subhedral single-crystal grains up to 0.5 mm across and up to 40 mu m thick. The colour and streak are black and the lustre is submetallic. The new mineral is brittle, with the Mohs' hardness of 6. No cleavage is observed. The fracture is uneven. The calculated density is 5.446 gcm-3. In reflected light, zincorinmanite-(Zn) is light grey, no pleochroism is observed. The reflectance values (Rmin, %/Rmax, %/lambda, nm) are: 12.6/13.7/470, 12.1/13.2/546, 11.8/12.8/589 and 11.5/12.2/650. The Raman spectrum shows bands corresponding to the O-H and Sb-O stretching vibrations and (Fe3+,M2+)-O-H bending modes. The chemical composition is (electron microprobe data, with iron divided into Fe2O3 and FeO based on the charge balance and H2O calculated from the structural data, wt.%): MgO 1.42, MnO 0.44, FeO 2.04, ZnO 22.55, Al2O3 1.95, Fe2O3 35.59, TiO2 1.51, Sb2O5 33.05, H2O 1.18, total 99.73. The empirical formula is [(Fe3+2.12Al0.18)(Zn0.32Mg0.16Fe2+0.13Mn0.03)Ti0.06]Sigma 3.00(Sb0.97Ti0.03)Sigma 1.00Zn1.00O7[(OH)0.61O0.39]Sigma 1.00. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R = 0.0191. Zincorinmanite-(Zn) is hexagonal, space group P63mc, a = 5.9720(1), c = 9.3578(1) & Aring; and V = 289.031(8) & Aring;3 (Z = 2). The new mineral is isostructural with other members of the nolanite group. The strongest lines of the powder X-ray diffraction pattern [d, & Aring; (I, %) - hkl] are: 5.176 (46) - 100; 3.473 (77) - 102; 2.989 (46) - 110; 2.674 (86) - 103; 2.520 (100) - 112; and 2.496 (42) - 201.