A re-examination of the El Dragón vein-type Se deposit using polarized light microscopy and scanning-electron microscopy combined with electron-microprobe analyses revealed the following results: the detection of (a) petříčekite, krut’aite and penroseite close to endmember composition; (b) a yet unknown mineral of the ideal composition CuNi2Se4; (c) intermediate members of the vaesite-pyrite solid-solution series; and (d) a mineral with a composition intermediate between athabascaite and its yet unknown S-equivalent, Cu4S5. Triggered by volcanic-hydrothermal activities around the Porco caldera, formation of the mineralization involved five episodes of fault formation and re-opening, fluid-mediated metal mobilization, metalliferous fluid infiltration, and mineral precipitation, re-deposition, and alteration that probably extended from 12 Ma until today. The origin of the Se-vein was accomplished by the multiple injection of highly oxidized, metal-rich fluids into a fault at the interface between black shale and siltstone. These low-T solutions (estimated max. temperature 100 °C, max. pressure 1 bar) possessed high to exceptionally Se fugacities (log fSe2 fluctuating between of −14.5 and −11.2) that prevailed for most of the evolution of the deposit, only interrupted once, during the episode of deposition of sulfides of Cu and Fe and resulting partial alteration of the pre-existing selenides. Formation of end-member krut’aite and native selenium implies a minimum log fSe2 of −11.2 at the final stage of vein formation. The likely source of Se and the accompanying metals (Cu, Ag, Ni, Co, Au, Pb, Hg, Cd, Fe and Bi) is the neighboring Kupferschiefer-type (possibly Devonian) black shale rich in framboidal pyrite, Cu-sulfide aggregates, and organic matter. Deposition of Se-minerals occurred where the oxidized metal-bearing solutions became in contact with a reductant, associated with the reduction of mobile selenate to immobile selenide or elemental Se.

Petříčekite, ideally CuSe₂, is a new mineral from the Předbořice deposit, Central Bohemia Region, Czech Republic. It occurs as rare inclusions, up to 150 μm across, in large eucairite grains closely associated with athabascaite/klockmannite and unknown selenide phases. Petříčekite is opaque with a metallic luster and shows a black streak. It is brittle; the Vickers hardness (VHN₁₅) is 33 kg/mm² (range: 28–40 kg/mm²) (Mohs hardness of ~2–2½). In reflected light, petříčekite is pale blue grey to pale pinkish, weakly pleochroic and weakly bireflectant from slightly blue-grey to slightly pinkish-grey. Under crossed polars, it is anisotropic with light grey-blue to light pink rotation tints. Internal reflections are absent. Reflectance percentages for the four COM (Commission on Ore Mineralogy) wavelengths (R_min and R_max) are 42.35, 41.8 (470 nm), 42.0, 42.2 (546 nm), 41.9, 42.35 (589 nm) and 42.05, 42.85 (650 nm), respectively. Petříčekite is orthorhombic, space group Pnnm, with a = 4.918(2) Å; b = 6.001(2) Å; c = 3.670(1) Å; V = 108.31(1) ų; Z = 2. The crystal structure (R1 = 0.0336 for 159 reflections with I > 2σ(I)) belongs to the marcasite-type structure. It consists of edge-sharing chains of CuSe₆ octahedra parallel to [001] linked by sharing Se₂ dimers. The Se–Se bonds are all parallel to (001). The five strongest powder-diffraction lines (d in Å (I/I₀) (hkl)) are: 2.938 (70) (101); 2.639 (100) (111); 2.563 (85) (120); 1.935 (70) (211); 1.834 (30) (002). The mean of nine electron-microprobe analyses on the crystal used for the structural study gave Ag 0.22(13), Cu 15.39(15), Hg 0.01(3), Pb 0.03(2), Fe 12.18(10), Pd 0.11(4), S 0.09(1), Se 71.61(29) and total 99.64(41) wt %, corresponding on the basis of a total of three atoms, to (Cu_0.53Fe_0.48)_Σ1.01(Se_1.98S_0.01)_Σ1.99. Additional crystals exhibiting higher Cu contents (up to 0.74 a.p.f.u.) were also investigated. The new mineral has been approved by the IMA-NMNC Commission (2015-111) and named after Václav Petříček, renowned crystallographer of the Institute of Physics of the Czech Academy of Sciences, Prague. Optical, compositional and structural properties confirm that nearly pure petříčekite also formed as late-stage mineral in the Se mineralization at El Dragón, Bolivia. It has end-member composition, Cu_0.99Se_2.00 (n = 5), and is typically associated with krut’aite of ideal composition, native selenium and goethite. Finally, optical and chemical data indicate that pure petříčekite is likely present also at Sierra de Cacheuta, Argentina.

Cerromojonite, ideally CuPbBiSe₃, represents a new selenide from the El Dragόn mine, Department of Potosí, Bolivia. It either occurs as minute grains (up to 30 µm in size) in interstices of hansblockite/quijarroite intergrowths, forming an angular network-like intersertal texture, or as elongated, thin-tabular crystals (up to 200 μm long and 40 μm wide) within lath-shaped or acicular mineral aggregates (interpreted as pseudomorphs) up to 2 mm in length and 200 μm in width. It is non-fluorescent, black, and opaque, with a metallic luster and black streak. It is brittle, with an irregular fracture, and no obvious cleavage and parting. In plane-polarized incident light, cerromojonite is grey to cream-white, and weakly pleochroic, showing no internal reflections. Between crossed polarizers, cerromojonite is weakly anisotropic, with rotation tints in shades of brown and grey. Lamellar twinning on {110} is common. The reflectance values in air for the COM standard wavelengths (R₁ and R₂) are: 48.8 and 50.3 (470 nm), 48.2 and 51.8 (546 nm), 47.8 and 52.0 (589 nm), and 47.2 and 52.0 (650 nm). Electron-microprobe analyses yielded a mean composition of: Cu 7.91, Ag 2.35, Hg 7.42, Pb 16.39, Fe 0.04, Ni 0.02, Bi 32.61, Se 33.37, total 100.14 wt %. The empirical formula (based on 6 atoms pfu) is (Cu_0.89Hg_0.11)_{Σ = 1.00}(Pb_0.56Ag_0.16Hg_0.15 Bi_0.11Fe_0.01)_{Σ = 0.99}Bi_1.00Se_3.01. The ideal formula is CuPbBiSe₃. Cerromojonite is orthorhombic (space group Pn2₁m), with a = 8.202(1) Å, b = 8.741(1) Å, c = 8.029(1) Å, V = 575.7(1) ų, Z = 4. Calculated density is 7.035 g·cm⁻³. The five strongest measured X-ray powder diffraction lines (d in Å (I/I₀) (hkl)) are: 3.86 (25) (120), 2.783 (100) (122), 2.727 (55) (212), 2.608 (40) (310), and 1.999 (25) (004). Cerromojonite is a new member of the bournonite group, representing the Se-analogue of součekite, CuPbBi(S,Se)₃. It is deposited from strongly oxidizing low-T hydrothermal fluids at a f_Se2/f_S2 ratio >1, both as primary and secondary phase. The new species has been approved by the IMA-CNMNC (2018-040) and is named for Cerro Mojon, the highest mountain peak closest to the El Dragón mine.

Tilkerodeite, ideally Pd₂HgSe₃, is a new platinum-group selenide from the Eskaborner Stollen (Adit Eskaborn) at Tilkerode, Harz Mountains, Germany. Tilkerodeite crystals occur as euhedral inclusions in tiemannite or as extremely fine-grained lamellar aggregates (grain-size up to 3 μm) in a dolomite–ankerite matrix, together with clausthalite, tiemannite, jacutingaite, stibiopalladinite, and native gold. Neighbouring Se-bearing minerals include tischendorfite and chrisstanleyite. Tilkerodeite is opaque with a metallic luster, and is flexible in blade-like crystals, with perfect basal cleavage $\left\{001\right\}$. In plane-polarized light, tilkerodeite is brownish-grey. It is weakly bireflectant, and weakly pleochroic in shades of light-brown and grey. The anisotropy is weak, with rotation tints in weak shades of greenish-brown and grey-brown. The range of reflectance is estimated in comparison to clausthalite with 45–50%. Electron-microprobe analyses yield the mean composition (wt. %) Se 32.68, Hg 26.33, Pt 20.62, Pd 15.89, Pb 2.72, Cu 0.66, S 0.27, total 99.17 wt. %. The empirical formula (based on six atoms pfu) is (Pd_1.08Pt_0.76Pb_0.09Cu_0.07)_Σ2.00Hg_0.95(Se_2.98S_0.07)_Σ3.05. The ideal formula is Pd₂HgSe₃. Tilkerodeite is trigonal, with Pt₄Tl₂Te₆-type structure, space group P$\bar{3}$m1, a = 7.325(9) Å, c = 5.288(6) Å, V = 245.7(9) ų, and Z = 2. It is the Pd-analogue of jacutingaite. Tilkerodeite formed hydrothermally, possibly involving the alteration of tiemannite by low-temperature oxidizing fluids. The new species has been approved by the IMA-CNMNC (2019-111) and is named after the locality. Tilkerode is the most important selenide-bearing occurrence in Germany and type locality of naumannite, eskebornite, and tischendorfite.

Quijarroite, ideally Cu₆HgPb₂Bi₄Se₁₂, is a new selenide species from the El Dragόn mine, Department of Potosí, Bolivia. It most frequently occurs as lath-shaped thin plates (up to 150 µm in length and 20 µm in width) intimately (subparallel) intergrown with hansblockite, forming an angular network-like intersertal texture. Quijarroite is occasionally also present as sub- to anhedral grains up to 200 µm in length and 50 µm in width. It is non-fluorescent, black and opaque with a metallic luster and black streak. It is brittle, with an irregular fracture and no obvious cleavage and parting. In plane-polarized incident light, quijarroite is weakly pleochroic from cream to very slightly more brownish-cream, displaying no internal reflections. Between crossed polars, quijarroite is moderately anisotropic with pale orange-brown to blue rotation tints. Lamellar twinning on {110} is common; parquet twinning occurs rarely. The reflectance values in the air for the COM (Commission on Ore Mineralogy) standard wavelengths (R₁ and R₂) are: 46.7, 46.8 (470 nm), 47.4, 48.2 (546 nm), 47.1, 48.5 (589 nm), and 46.6, 48.7 (650 nm). Electron-microprobe analyses yielded a mean composition of Cu 13.34, Ag 1.02, Hg 7.67, Pb 16.87, Co 0.03, Ni 0.15, Bi 27.65, Se 33.52, total 100.24 wt %. The mean empirical formula, normalized to 25 apfu (atoms per formula unit), is (Cu_5.84Ag_0.26)_{Σ = 6.10}(Hg_1.06Ni_0.07Co_0.01)_{Σ = 1.14}Pb_2.27Bi_3.68Se_11.81 (n = 24). The simplified formula is Cu₆HgPb₂Bi₄Se₁₂. Quijarroite is orthorhombic, space group Pmn2₁, with a = 9.2413(8), b = 9.0206(7), c = 9.6219(8) Å, V = 802.1(1) ų, Z = 1. The calculated density is 5.771 g·cm⁻³. The five strongest X-ray powder-diffraction lines (d in Å (I/I₀) (hkl)) are: 5.36 (55) (111), 3.785 (60) (211), 3.291 (90) (022), 3.125 (100) (212), and 2.312 (50) (400). The crystal structure of quijarroite can be considered a galena derivative and could be derived from that of bournonite. It is a primary mineral, deposited from an oxidizing low-T hydrothermal fluid at a $f_{{Se}_2}$ / $f_{S_2}$ ratio greater than unity. The new species has been approved by the IMA-CNMNC (2016-052) and is named for the Quijarro Province in Bolivia, in which the El Dragón mine is located.

The Sierra de Cacheuta vein-type Se mineralization in the Mendoza Province predominantly consists of clausthalite, klockmannite, eskebornite, eucairite, and naumannite. These primary selenides formed in a fault zone, cutting through fine-grained trachytic host rock. Cross-sections perpendicular to the veinlets, polarized light microscopy, and scanning-electron microscopy, combined with electron-microprobe analysis, provide a record of the relationship between different crystallization and deformation events. Mineralization encompasses four episodes of fault formation (d1–d4): early zonal selenide crystallization (stage (I)); ductile deformation of the selenides (stage (II)); fault re-opening, fluid-mediated metal mobilization, metalliferous-fluid infiltration, and mineral precipitation (stage (III)); and subsequent alteration (stage (IV)). The Se vein originated from multiple injections of highly oxidized, metal-rich fluids. These low-T solutions (estimated max. temperature 100 °C, max. pressure 1 bar) possessed high to exceptionally high Se fugacities (log f_Se2 between −14.5 and −11.2) that prevailed for most of the evolution of the deposit. The source of the Se and the accompanying metals (Cu, Ag, Pb, and Fe) is probably the neighboring bituminous shale. The deposition of Se minerals occurred when the oxidized metal-bearing solutions came in contact with a reductant, which caused the reduction of mobile selenate to immobile selenide or elemental Se. We identified several features that permit us to safely distinguish samples from Cacheuta from Argentinian Se deposits in the Province of La Rioja: (I) trachytic host rock fragments containing bitumen and TiO₂ pseudomorphs after titanomagnetite; (II) early Co-rich and Ni-poor krut’aite (Co < 6.7 wt %, Ni < 1.2 wt %) partly replaced by clausthalite, umangite, klockmannite, eskebornite, Ni-poor tyrrellite (Ni < 2.7 wt %), Ni-poor trogtalite (Ni < 1.2 wt %), and end-member krut’aite and petříčekite; (III) lack of calcite gangue; and (VI) Se-bearing alteration minerals comprising chalcomenite, molybdomenite, cobaltomenite, an unnamed Cu selenide (for which the ideal formula may be either Cu₂Se₃ or Cu₅Se₈), and possibly mandarinoite, mereheadite, orlandiite, and scotlandite as new species for this occurrence.