Selenium mineralization in the Příbram uranium and base-metal district (Central Bohemia, Czech Republic) bound to uraninite occurrences in calcite hydrothermal veins is extremely diverse. The selenides antimonselite, athabascaite, bellidoite, berzelianite, brodtkorbite, bukovite, bytízite, cadmoselite, chaméanite, clausthalite, crookesite, dzharkenite, eskebornite, eucairite, ferroselite, giraudite, hakite, klockmannite, naumannite, permingeatite, příbramite, sabatierite, tiemannite, and umangite were found here, including two new mineral phases: Hg-Cu-Sb and Cu-As selenides. Those selenides—and in some cases their sulphidic equivalents—are characterized using wavelength-dispersive spectroscopy, reflected light, powder X-ray diffraction, single crystal X-ray diffraction, Raman spectroscopy, and electron backscatter diffraction. The selenide mineralization in the Příbram uranium district is bound to the border of the carbonate-uraninite and subsequent carbonate-sulphidic stages. Selenides crystallized there at temperatures near 100 °C in the neutral-to-weakly-alkaline environment from solutions with high oxygen fugacity and a high Se₂/S₂ fugacity ratio.

The crystal structure, elastic properties and the Raman spectrum of the layered calcium uranyl silicate pentahydrate mineral uranophane-β, Ca(UO₂)₂Si₂O₆(OH)₂·5H₂O, are studied by means of first-principles solid-state methods and compared with the corresponding information for the α polymorph. The availability of the energy optimized full crystal structure of uranophane-β, including the positions of the hydrogen atoms, made possible the computation of its elastic properties and the Raman spectrum by using the theoretical methodology. An extended set of relevant mechanical data is reported. Uranophane-β is shown to be a weak and ductile mineral and, consequenty, is mechanically very different from the α polymorph which is a hard and brittle material. Uranophane-β exhibits the important negative Poisson's ratio (NPR) and negative linear compressibility (NLC) phenomena. The experimental Raman spectrum of uranophane-β obtained from a natural mineral sample from pegmatite Perus, São Paulo, Brazil, is compared with the spectrum determined theoretically. Since both spectra are in very good agreement, the theoretical methods are employed to assign the Raman spectrum. Three weak bands of the experimental spectrum of this mineral, located at the wavenumbers 2302, 2128 and 2042 cm⁻¹, are identified as combination bands. The Raman spectrum of uranophane-β is also compared with that of the α polymorph. While they are rather similar, a detailed analysis reveals a significant number of differences. Finally, the relative thermodynamic stability of the α and β polymorphs is evaluated. The α polymorph is more stable than the β polymorph at zero pressure and temperature by −12.0 kJ mol⁻¹.

The crystal structure, hydrogen bonding, mechanical properties and Raman spectrum of the lead uranyl silicate monohydrate mineral kasolite, Pb(UO₂)(SiO₄)·H₂O, are investigated by means of first-principles solid-state methods based on density functional theory using plane waves and pseudopotentials. The computed unit cell parameters, bond lengths and angles and X-ray powder pattern of kasolite are found to be in very good agreement with their experimental counterparts. The calculated hydrogen atom positions and associated hydrogen bond structure in the unit cell of kasolite confirmed the hydrogen bond scheme previously determined from X-ray diffraction data. The kasolite crystal structure is formed from uranyl silicate layers having the uranophane sheet anion-topology. The lead ions and water molecules are located in the interlayer space. Water molecules belong to the coordination structure of lead interlayer ions and reinforce the structure by hydrogen bonding between the uranyl silicate sheets. The hydrogen bonding in kasolite is strong and dual, that is, the water molecules are distributed in pairs, held together by two symmetrically related hydrogen bonds, one being directed from the first water molecule to the second one and the other from the second water molecule to the first one. As a result of the full structure determination of kasolite, the determination of its mechanical properties and Raman spectrum becomes possible using theoretical methods. The mechanical properties and mechanical stability of the structure of kasolite are studied using the finite deformation technique. The bulk modulus and its pressure derivatives, the Young and shear moduli, the Poisson ratio and the ductility, hardness and anisotropy indices are reported. Kasolite is a hard and brittle mineral possessing a large bulk modulus of the order of B ∼ 71 GPa. The structure is mechanically stable and very isotropic. The large mechanical isotropy of the structure is unexpected since layered structures are commonly very anisotropic and results from the strong dual hydrogen bonding among the uranyl silicate sheets. The experimental Raman spectrum of kasolite is recorded from a natural mineral sample from the Jánská vein, Příbram base metal ore district, Czech Republic, and determined by using density functional perturbation theory. The agreement is excellent and, therefore, the theoretical calculations are employed to assign the experimental spectrum. Besides, the theoretical results are used to guide the resolution into single components of the bands from the experimental spectrum. A large number of kasolite Raman bands are reassigned. Three bands of the experimental spectrum located at the wavenumbers 1015, 977 and 813 cm⁻¹, are identified as combination bands.

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 Ag_6.27[(Ag_3.90Cu_0.38)_Σ4.28(Zn_1.60Fe_0.09Cd_0.03)_Σ1.72]_Σ6.00(As_2.26Sb_1.48)_Σ3.74S_12.50. 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) ų 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 (R_obs = 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).

Significant selenium enrichment associated with selenides and previously unknown Ag-Pb-Sb, Ag-Sb and Pb-Sb sulfosalts has been discovered in hydrothermal ore veins in the Anthony of Padua mine near Poličany, Kutná Hora ore district, central Bohemia, Czech Republic. The ore mineralogy and crystal chemistry of more than twenty silver minerals are studied here. Selenium mineralization is evidenced by a) the occurrence of selenium minerals, and b) significantly increased selenium contents in sulfosalts. Identified selenium minerals include aguilarite and selenides naumannite and clausthalite. The previously unknown sulfosalts from Kutná Hora are identified: Ag-excess fizélyite, fizélyite, andorite IV, andorite VI, unnamed Ag-poor Ag-Pb-Sb sulfosalts, semseyite, stephanite, polybasite, unnamed Ag-Cu-S mineral phases and uytenbogaardtite. Among the newly identified sulfides is argyrodite; germanium is a new chemical element in geochemistry of Kutná Hora. Three types of ore were recognized in the vein assemblage: the Pb-rich black ore (i) in quartz; the Ag-rich red ore (ii) in kutnohorite-quartz gangue; and the Ag-rich ore (iii) in milky quartz without sulfides. The general succession scheme runs for the Pb-rich black ore (i) as follows: galena – boulangerite (– jamesonite) – owyheeite – fizélyite – Ag-exces fizélyite – andorite IV – andorite VI – freieslebenite – diaphorite – miargyrite – freibergite. For the Ag-rich red ore (ii) and ore (iii) the most prominent pattern is: galena – diaphorite – freibergite – miargyrite – pyragyrite – stephanite – polybasite – acanthite. The parallel succession scheme progresses from Se-poor to Se-rich phases, i.e., galena – members of galena – clausthalite solid solution – clausthalite; miargyrite – Se-rich miargyrite; acanthite – aguilarite – naumannite. A likely source of selenium is in the serpentinized ultrabasic bodies, known in the area of “silver” lodes in the South of the ore district, which may enable to pre-concentrate selenium, released into hydrothermal fluids during tectonic events. The origin of the studied ore mineralization is primarily bound to the youngest stage of mineralization of the whole ore district, corresponding to the Ag-Sb sequence of the ‘eb’ ore type of the Freiberg ore district in Saxony (Germany) and shows mineralogical and geochemical similarities to low-sulfidation epithermal-style Ag-Au mineralization.