Selenium-rich Au–Ag mineralization has been discovered in the Kremnica ore district, central Slovakia. The mineralization is hosted by a single quartz–dolomite vein hosted by Neogene propyllitized andesites of the Kremnica stratovolcano. Ore mineralogy and crystal chemistry of individual ore minerals have been studied here. The early base-metal ore mineralization composed of pyrite, sphalerite, and chalcopyrite lacks selenium, whereas the superimposed Au–Ag paragenesis is Se-enriched. The Au–Ag alloys, uytenbogaardtite, minerals of the galena–clausthalite series, acanthite–naumannite series, diaphorite, miargyrite, pyrargyrite–proustite, polybasite group, minerals of the tetrahedrite group and andorite branch (andorite IV, andorite VI, Ag-excess fizélyite), freieslebenite, and rare Pb–Sb sulphosalts (scaiinite, robinsonite, plagionite) have been identified here. Besides selenides, the most Se-enriched phases are miargyrite, proustite–pyrargyrite, and polybasite–pearceite, whose Se contents are among the highest reported worldwide. In addition, one new phase has been found, corresponding to a Se-analogue of pearceite containing 2.08–3.54 apfu Se. The style of mineralization, paragenetic situation, and chemical trends observed in individual minerals are comparable to those of Au–Ag low-sulphidation epithermal Au–Ag mineralizations of the Kremnica and neighboring Štiavnica and Hodruša-Hámre ore districts. However, the pronounced enrichment in selenium is a specific feature of the studied vein only.

The new mineral grimmite, NiCo₂S₄, was found in siderite–sphalerite gangue at the dump of shaft no. 9, one of the mines in the abandoned Příbram uranium and base-metal district, central Bohemia, Czech Republic. The new mineral occurs as rare idiomorphic to hypidiomorphic grains up to 200 µm × 70 µm in size or veinlet aggregates. In reflected light, grimmite is creamy grey with a pinkish tint. Pleochroism, polarising colours and internal reflections were not observed. Reflectance values of grimmite in the air (R %) are 42.5 at 470 nm, 45.9 at 546 nm, 47.7 at 589 nm and 50.2 at 650 nm). The empirical formula for grimmite, based on electron-microprobe analyses (n= 13), is Ni_1.01(Co_1.99Fe_0.06Pb_0.01Bi_0.01)_Σ2.07S_3.92. The ideal formula is NiCo₂S₄; requires Ni 19.26, Co 38.67, and S 42.07; and totals 100.00 wt %. According to the single-crystal X-ray diffraction data (R_obs=0.0489), grimmite is cubic, Fd–3m, a=9.3933(9), with V=828.81(14) ų and Z=8. The calculated density is 4.96 g cm⁻³. The strongest reflections of the calculated powder X-ray diffraction pattern [d, Å (I)(hkl)] are 3.3210 (75) (220), 2.7116 (7) (222), 2.3483 (81) (400), 1.9174 (27) (422), 1.6605 (100) (440), 1.4852 (11) (620) and 1.3558 (15) (444). Grimmite is named after Johann Grimm (24 June or 24 July 1805 to 26 June 1874), the former director of the Příbram Mining College. The association of sulfides and sulfarsenides was found with grimmite. Essentially non-zoned coarse-grained siderite encloses idiomorphic crystals and/or aggregates of red sphalerite I and zoned skutterudite-group minerals. Skutterudites (skutterudite, niklskutterudite and ferroskutterudite) are usually strongly corroded and replaced by younger phases. Relics of skutterudite are rimmed by nickeline and later on by gersdorffite with rare domains of glaucodot and arsenopyrite, whereas completely leached parts of skutterudite crystals are filled up by quartz containing small isolated grains and aggregates of pyrite, sphalerite II, grimmite, galena, ullmannite, bismuthinite, parkerite and jaipurite, the latter being rarely enclosed in grimmite.

This mineralogical and fluid inclusion study was conducted on an Au-bearing quartz–sulfide vein encountered in the deep parts of the Bytíz deposit in the Příbram uranium and base-metal district, Bohemian Massif, Czech Republic. The samples were taken where the Au-bearing vein is crosscut by the common base-metal Zn-Pb ore vein Bt23C. The early mineralization of the Au-bearing vein is composed mainly of quartz (Q-1 to Q-3), illite–muscovite, Fe-Mg chlorite, arsenopyrite, and Au-Ag alloys, showing a wide range of compositions (4–69 at. % Ag) and a decrease in Au/(Au + Ag) ratios during vein evolution. Younger hydrothermal processes led to the crystallization of nests and veinlets composed of late quartz (Q-4), carbonates (siderite, dolomite–ankerite and calcite), base-metal sulfides (galena, sphalerite, chalcopyrite, and tetrahedrite), a suite of Ag and Bi-tellurides, and acanthite. The input of Sb is manifested by the partial to complete replacement of some gold grains by aurostibite and an unnamed (Ag,Au)-Sb oxide with a composition close to AuSbO₃. The fluid inclusion study, combined with chlorite thermometry and arsenopyrite thermometry, showed that the early mineralization crystallized from progressively cooled (from 300 to 400 °C down to ca. 180 °C), diluted (1.2–7.0 wt. % NaCl eq.) aqueous solutions. The late portion of the mineralization formed from aqueous fluids with highly variable salinity (0.2–23.4 wt. % NaCl eq.) and homogenization temperatures decreasing from ca. 250 °C to < 50 °C, which compare well with the base-metal mineralization of the vein Bt23C and other base-metal veins of the Příbram ore area. Our study illustrates the nature and intensity of the processes of the reworking of the early gold mineralization mediated by the younger Ag,Sb-rich base-metal fluids, giving rise to Příbram’s typical late-Variscan vein Zn-Pb mineralization.

Selenium-rich Au-Ag mineralization has been discovered in the Kremnica ore district, central Slovakia. The mineralization is hosted by a single quartz-dolomite vein hosted by Neogene propyllitized andesites of the Kremnica stratovolcano. Ore mineralogy and crystal chemistry of individual ore minerals have been studied here. The early base-metal ore mineralization composed of pyrite, sphalerite and chalcopyrite lacks selenium, whereas the superimposed Au-Ag paragenesis is Se-enriched. The Au-Ag alloys, uytenbogaardtite, minerals of the galena-clausthalite series, acanthite-naumannite series, diaphorite, miargyrite, pyrargyrite-proustite, polybasite group, minerals of the tetrahedrite group and andorite branch (andorite IV, andorite VI, Ag-excess fizélyite), freislebenite, and rare Pb-Sb sulphosalts (scaiinite, robinsonite, plagionite) have been identified here. Besides selenides, the most Se-enriched phases are miargyrite, proustite-pyrargyrite, and polybasite-pearceite, whose Se contents are among the highest reported worldwide. In addition, one new phase has been found, corresponding to a Se-analogue of pearceite containing 2.08 - 3.54 apfu Se. The style of mineralization, paragenetic situation, and chemical trends observed in individual minerals are comparable to those of Au-Ag low-sulphidation epithermal Au-Ag mineralizations of the Kremnica and neighboring Štiavnica and Hodruša-Hámre Ore Districts, however, the pronounced enrichment in selenium is a specific feature of the studied vein only.

The Václav vein (Březové Hory deposit, Příbram ore area, Czech Republic) is a base–metal vein containing minor Cu-Zn-Pb-Ag-Sb sulfidic mineralization in a usually hematitized gangue. A detailed mineralogical study using an electron microprobe revealed a complicated multistage evolution of the vein. Early siderite and Fe-rich dolomite were strongly replaced by assemblages of hematite+rhodochrosite and hematite+kutnohorite/Mn-rich dolomite, respectively. In addition, siderite also experienced strong silicification. These changes were associated with the dissolution of associated sulfides (sphalerite, galena). The following portion of the vein contains low-Mn dolomite and calcite gangue with Zn-rich chlorite, wittichenite, tetrahedrite-group minerals, chalcopyrite, bornite, and djurleite, again showing common replacement textures in case of sulfides. The latest stage was characterized by the input of Ag and Hg, giving rise to Ag-Cu sulfides, native silver (partly Hg-rich), balkanite, and (meta)cinnabar. We explain the formation of hematite-bearing oxidized assemblages at the expense of pre-existing “normal” Příbram mineralization due to repeated episodic infiltration of oxygenated surface waters during the vein evolution. Episodic mixing of ore fluids with surface waters was suggested from previous stable isotope and fluid inclusion studies in the Příbram ore area. Our mineralogical study thus strengthens this genetic scenario, illustrates the dynamics of fluid movement during the evolution of a distinct ore vein structure, and shows that the low content of ore minerals cannot be necessarily a primary feature of a vein.