Search Results (16)

Mineral characterization of gold-bearing metasomatites in the Khaptasynnakh ore zone of the Anabar Shield is provided in detail. The following ore formation sequence of mineral associations in the Khaptasynnakh zone was found: pyrite and pyrrhotite → gersdorffite and molybdenite → chalcopyrite, sphalerite, and galena → bornite and chalcocite → tellurides, native gold, stibnite, cinnabar, and native bismuth. Native gold is characterized by varying fineness (550 to 926‰) and Cu impurity (up to 7.87%) values. Most often, it forms symplectite intergrowths with Au telluride–calaverite. Native gold and Au tellurides showed inclusions of chalcocite, bornite, altaite, tellurobismuthite, rickardite, petzite, and clausthalite. A two-stage formation process of the examined gold is suggested: Low-fineness gold was introduced into the system during early potassium metasomatism, while higher-fineness gold related to silica metasomatism resulted from its additional mobilization by fluid during late-stage formation. The low-temperature gold–telluride association observed in the mineral paragenesis of ore-bearing rocks, as well as its inclusions in native gold, suggests epithermal gold–telluride mineralization. Mineral inclusions examined in placer gold validate a genetic relation between the examined ores and gold placers in the Khaptasynnakh ore zone. Full article

This study aims to investigate the depositional environment, sediment sources, and elemental occurrence of Upper Paleozoic coal in the Renjiazhuang Mining District, Western Ordos Basin. Furthermore, SEM-EDX, optical microscope (OM), ICP-AES, ICP-MS, and AAS were used. Compared with hard coal of the world, M3 coals were enriched in Ga, Li, Zr, Be, Ta, Hf, Nb, Pb, and Th, M5 coals were enriched in Li (CC = 10.21), Ta (CC = 6.96), Nb (CC = 6.95), Be, Sc, Ga, Hf, Th, Pb, Zr, In, and REY, while M9 coals were enriched in Li (CC = 14.79), Ta (CC = 5.41), Ga, W, Hf, Nb, Zr, Pb, and Th. In addition, minerals were mainly composed of kaolinite, dolomite, pyrite, feldspar, calcite, and quartz, locally visible minor amounts of monazite, zircon, clausthalite, chalcopyrite, iron dolomite, albite, fluorite, siderite, galena, barite, boehmite, and rutile. In addition, maceral compositions of M3 coals and M9 coals were dominated by vitrinite (up to 78.50%), while M5 coals were the main inertite (up to 76.26%), and minor amounts of liptinite. REY distribution patterns of all samples exhibited light REY enrichment and negative Eu anomalies. The geochemistry of samples (TiO₂ and Al₂O₃, Nb/Y and Zr × 0.0001/TiO₂ ratios, and REY enrichment types) indicates that the sediment sources of samples originated from felsic igneous rocks. Indicator parameters (TPI, GI, VI, GWI, V/I, Sr/Ba, Th/U, and Ce_N/Ce_N*) suggest that these coals were formed in different paleopeat swamp environments: M3 coal was formed in a lower delta plain and terrestrial (lacustrine) facies with weak oxidation and reduction, and M5 coal was formed in a terrestrial and dry forest swamp environment with weak oxidation–oxidation, while M9 coal was formed in a seawater environment of humid forest swamps and the transition from the lower delta plain to continental sedimentation with weak oxidation and reduction. Statistical methods were used to study the elemental occurrence. Moreover, Li, Ta, Hf, Nb, Zr, Pb, and Th elements were associated with aluminosilicates, and Ga occurred as silicate. Full article

In the last few years, a controversy has been raised regarding the nature of the chemical bonding present in phase change materials (PCMs), many of which are minerals such as galena (PbS), clausthalite (PbSe), and altaite (PbTe). Two opposite bonding models have claimed to be able to explain the extraordinary properties of PCMs in the last decade: the hypervalent (electron-rich multicenter) bonding model and the metavalent (electron-deficient) bonding model. In this context, a third bonding model, the electron-deficient multicenter bonding model, has been recently added. In this work, we comment on the pros and cons of the hypervalent and metavalent bonding models and briefly review the three approaches. We suggest that both hypervalent and metavalent bonding models can be reconciled with the third way, which considers that PCMs are governed by electron-deficient multicenter bonds. To help supporters of the metavalent and hypervalent bonding model to change their minds, we have commented on the chemical bonding in GeSe and SnSe under pressure and in several polyiodides with different sizes and geometries. Full article

Several Jurassic, ophiolite-hosted Cu-Zn VMS deposits occur in Tuscany. They are hosted by tectonic units of oceanic affinity (Ligurian Units), such as the well-known deposits of nearby Liguria. Industrial production was small and definitively ceased in the 1960s. Locally, massive ore (chalcopyrite-bornite-chalcocite) with an exceptionally high grade was found. The Montecatini Val di Cecina mine exploited the largest “bonanza” and, for few decades in the 19th century, became one of the most profitable copper mines in Europe. This study provides an updated review of these deposits. Tuscan Cu-Zn VMSs mostly occur in proximity of the contact between the serpentinite-gabbro basement and the overlying basalts. Chalcopyrite-pyrite stockworks occur in serpentinite-gabbro cut by dolerite dykes, while the largest massive sulphide bodies are hosted by polymictic-monomictic breccias at the base of pillow basalts. Early chalcopyrite ores were mechanically–chemically reworked and upgraded to bornite-rich nodular ore embedded in a chlorite, calcic amphibole, Fe-rich serpentine, quartz, andradite, ilvaite, and xonotlite assemblage. This bornite-rich ore contains substantial amount of sphalerite and pyrite and ubiquitous grains of clausthalite, hessite, tellurium, and gold. They represent a prime example of the sub-seafloor portion of a hybrid mafic-ultramafic oceanic hydrothermal system formed in an OCC along the slow spreading ridge of the Jurassic Piedmont-Ligurian Ocean. The peculiar mineralogical–textural character of the bornite-rich ore was driven by an interface coupled dissolution–precipitation process mediated by fluids. Full article

The research interest for many authors has been focused on the origin, recovery, and exploration of critical metals, including platinum-group elements (PGEs), with the aim of finding new potential sources. Many giant porphyry Cu deposits are well known around the Pacific Rim, in the Balkan–Carpathian system, Himalayas, China, and Malaysia. However, only certain porphyry Cu-Au deposits are characterized by the presence of significant Pd and Pt contents (up to 20 ppm). This contribution provides new analytical data on porphyry-Cu-Au±Pd±Pt deposits from the Chalkidiki Peninsula and an overview of the existing geochemical characteristics of selected porphyry-Cu deposits worldwide in order to define significant differences between PGE-fertile and PGE-poor porphyry-Cu intrusions. The larger Mg, Cr, Ni, Co, and Re contents and smaller LILE elements (Ba and Sr) in fertile porphyry-Cu-Au-(PGE) reflect the larger contribution from the mantle to the parent magmas. In contrast, the smaller Mg, Cr, Ni, Co, and Re contents and larger Ba and Sr in PGE-poor porphyry-Cu-Mo deposits from the Chalkidiki Peninsula (Vathi, Pontokerasia, and Gerakario) and Russia–Mongolia suggest the presence of parent magmas with a more crustal contribution. Although there is an overlap in the plots of those elements, probably due to the evolution of the ore-forming system, consideration of the maximum contents of Mg, Cr, Ni, and Co is proposed. Magnetite which separated from the mineralized Skouries porphyry of Greece showed small negative Eu anomalies (Eu/Eu* ≥ 0.55), reflecting a relatively high oxidation state during the cooling of the ore-forming system. The relatively high, up to 6 ppm (Pd+Pt), and low Cr content towards the transition from the porphyry to epithermal environment, coupled with the occurrence of Pd, Te, and Se minerals (merenskyite, clausthalite), and tetrahedrite–tennantite in fertile porphyry Cu deposits (Elatsite deposit, Bulgaria), reflect a highly fractionated ore-forming system. Thus, in addition to the crustal and mantle recycling, metasomatism, high oxidation state, and abundant magmatic water, other factors required for the origin of fertile porphyry-Cu deposits are the critical degree of mantle melting to release Pt and Pd in the ore-forming fluids and the degree of fractionation, as reflected in the mineral chemistry and geochemical data. Full article

The evolution characteristics of hydrothermal activity and superimposed uranium mineralization in the Qianjiadian ore field in southwestern Songliao Basin are still controversial and lack direct evidence. In this comprehensive study, a detailed identification of dolerite and hydrothermally altered un-mineralized sandstone and sandstone-hosted ore in the Yaojia Formation have been performed through the use of scanning electron microscopy observation, electron probe, carbon-oxygen-sulfur isotope, and fluid inclusion analyses. The results show that the hydrothermal fluid derived from the intermediate-basic magma intrusion is a low-temperature reducing alkaline fluid and rich in CO₂, Si, Zr, Ti, Fe, Mg, Mn, and Ca, producing different types of altered mineral assemblages in the rocks, including carbonation, pyritization, sphalerite mineralization, clausthalite mineralization, silicification, and biotitization. Specifically, the carbonate minerals in sandstone are mixed products of deep hydrothermal fluid and meteoric water, with carbon and oxygen isotopes ranging from −5.2‰ to −1.7‰ and −20.4‰ to −11.1‰, respectively. Carbon source of the carbonate minerals in dolerite is mainly inorganic carbon produced at the late stage of intermediate-basic magma evolution, with carbon and oxygen isotopes from −16.1‰ to −7.2‰ and −18.2‰ to −14.5‰, respectively. Various carbonate minerals in the rocks may have been precipitated by the hydrothermal fluid after the magmatic stage, due to the change of its CO₂ fugacity, temperature, and cation concentration during the long-term evolution stage. A series of carbonate minerals were generated as calcite, dolomite, ankerite, ferromanganese dolomite, and dawsonite. The precipitation processes and different types of carbonate mineral mixtures identified in this study mainly occur as parallel, gradual transition, interlacing, or inclusion metasomatism in the same vein body, without obvious mineralogical and petrologic characteristics of penetrating relationship. Homogenization temperature of fluid inclusions in calcite is high, in the range of 203–234 °C, with a low salinity of 0.71–4.34% NaCl, and the data range is relatively concentrated. Homogenization temperature of fluid inclusions in ankerite is usually low, ranging from 100 °C to 232 °C, with a high salinity of 4.18–9.98% NaCl. The precipitation processes of carbonate minerals and the results of this study are basically in consistent. Overall, the sandstone-type uranium deposits have a temporal and genetic relationship with hydrothermal activities during Paleogene. (1) Hydrothermal activity was directly involved in uranium mineralization, result in dissolution and reprecipitation of earlier uranium minerals, forming uranium-bearing ankerite and complexes containing uranium, zirconium, silicon, and titanium. (2) Hydrothermal fluid activity provided reducing agent to promote hydrocarbon generation from pyrolysis of carbonaceous fragments and accelerate uranium precipitation rate. (3) Regional water stagnation prolongs reaction time, contributing to huge uranium enrichment. This study provides new petrologic, mineralogical, and geochemical evidence for multi-fluid coupled and superimposed mineralization of sandstone-hosted uranium deposits in the sedimentary basin. Full article

Highly atypical mineralization involving Pd-Pt, Au-Ag, REE, Y, Zr, U, Th, and Cl-F-enriched minerals is found in zones with base metal sulfides (BMS; ~5 vol.% to 20 vol.%) in the eastern portion of the Oktyabrsky deposit in the Norilsk complex (Russia). The overall variations in Mg# index, 100 Mg/(Mg + Fe²⁺ + Mn), in host-rock minerals are 79.8 → 74.1 in olivine, 77.7 → 65.3 in orthopyroxene, 79.9 → 9.2 in clinopyroxene, and An_79.0 → An_3.7. The span of clinopyroxene and plagioclase compositions reflects their protracted crystallization from early magmatic to late interstitial associations. The magnesian chromite (Mg# 43.9) trends towards Cr-bearing magnetite with progressive buildups in oxygen fugacity; ilmenite varies from early Mg-rich to late Mn-rich variants. The main BMS are chalcopyrite, pyrrhotite, troilite, and Co-bearing pentlandite, with less abundant cubanite (or isocubanite), rare bornite, Co-bearing pyrite, Cd-bearing sphalerite (or wurtzite), altaite, members of the galena-clausthalite series and nickeline. A full series of Au-Ag alloy compositions is found with minor hessite, acanthite and argentopentlandite. The uncommon assemblage includes monazite-(Ce), thorite-coffinite, thorianite, uraninite, zirconolite, baddeleyite, zircon, bastnäsite-(La), and an unnamed metamict Y-dominant zirconolite-related mineral. About 20 species of PGM (platinum group minerals) were analyzed, including Pd-Pt tellurides, bismuthotellurides, bismuthides and stannides, Pd antimonides and plumbides, a Pd-Ag telluride, a Pt arsenide, a Pd-Ni arsenide, and unnamed Pd stannide-arsenide, Pd germanide-arsenide and Pt-Cu arseno-oxysulfide. The atypical assemblages are associated with Cl-rich annite with up to 7.54 wt.% Cl, Cl-rich hastingsite with up 4.06 wt.% Cl, ferro-hornblende (2.53 wt.% Cl), chlorapatite (>6 wt.% Cl) and extensive solid solutions of chlorapatite, fluorapatite and hydroxylapatite, Cl-bearing members of the chlorite group (chamosite; up to 0.96 wt.% Cl), and a Cl-bearing serpentine (up to 0.79 wt.% Cl). A decoupling of Cl and F in the geochemically evolved system is evident. The complex assemblages formed late from Cl-enriched fluids under subsolidus conditions of crystallization following extensive magmatic differentiation in the ore-bearing sequences. Full article

Mineralization of Te and Se was found in gold deposits and uranium occurrences, located in the Paleoproterozoic greenstone belts in Northern Fennoscandia. These deposits are of different genesis, but all of them formed at the late stages of the Svecofennian orogeny, and they have common geochemical association of metals Au, Cu, Co, U, Bi, Te, and Se. The prevalent Te minerals are Ni and Fe tellurides melonite and frohbergite, and Pb telluride altaite. Bismuth tellurides were detected in many deposits in the region, but usually not more than in two–three grains. The main selenide in the studied deposits is clausthalite. The most diversified selenium mineralization (clausthalite, klockmannite, kawazulite, skippenite, poubaite) was discovered in the deposits, located in the Russian part of the Salla-Kuolajarvi belt. Consecutive change of sulfides by tellurides, then by selenotellurides and later by selenides, indicates increase of selenium fugacity, fSe₂, in relation to fTe₂ and to fS₂in the mineralizing fluids. Gold-, selenium-, and tellutium-rich fluids are potentially linked with the post-Svecofennian thermal event and intrusion of post-orogenic granites (1.79–1.75 Ga) in the Salla-Kuolajarvi and Perapohja belts. Study of fluid inclusions in quartz from the deposits in the Salla-Kuolajarvi belt showed that the fluids were high-temperature (240–300 °C) with high salinity (up to 26% NaCl-eq.). Composition of all studied selenotellurides, kawazulite-skippenite, and poubaite varies significantly in Se/Te ratio and in Pb content. Skippenite and kawazulite show the full range of Se-Te isomorphism. Ni-Co and Co-Fe substitution plays an important role in melonite and mattagamite: high cobalt was detected in nickel telluride in the Juomasuo and Konttiaho, and mattagamites from Ozernoe and Juomasuo contain significant Fe. In the Ozernoe uranium occurrence, the main mineral-concentrator of selenium is molybdenite, which contains up to 16 wt.% of Se in the marginal parts of the grains. The molybdenite is rich in Re (up to 1.2 wt.%), and the impurity of Re is irregularly distributed in molybdenite flakes and spherulites. Full article

The trace element (TS) composition of isocubanite, chalcopyrite, pyrite, bornite, and covellite from oxidized Cu-rich massive sulfides of the Ashadze-2 hydrothermal field (12°58′ N, Mid-Atlantic Ridge) is studied using LA-ICP-MS. The understanding of TE behavior, which depends on the formation conditions and the mode of TE occurrence, in sulfides is important, since they are potential sources for byproduct TEs. Isocubanite has the highest Co contents). Chalcopyrite concentrates most Au. Bornite has the highest amounts of Se, Sn, and Te. Crystalline pyrite is a main carrier of Mn. Covellite after isocubanite is a host to the highest Sr, Ag, and Bi contents. Covellite after pyrite accumulates V, Ga and In. The isocubanite+chalcopyrite aggregates in altered gabrro contain the highest amounts of Ni, Zn, As, Mo, Cd, Sb (166 ppm), Tl, and Pb. The trace element geochemistry of sulfides is mainly controlled by local formation conditions. Submarine oxidation results in the formation of covellite and its enrichment in most trace elements relative to primary sulfides. This is a result of incorporation of seawater-derived elements and seawater-affected dissolution of accessory minerals (native gold, galena and clausthalite). Full article

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. Full article

Sulphide ores hosted in deeper parts of ophiolite complexes may be related to either primary magmatic processes or links to hydrothermal alteration and metal remobilization into hydrothermal systems. The Pindos ophiolite complex was selected for the present study because it hosts both Cyprus-type sulphides (Kondro Hill) and Fe–Cu–Co–Zn sulphides associated with magnetite (Perivoli-Tsoumes) within gabbro, close to its tectonic contact with serpentinized harzburgite, and thus offers the opportunity to delineate constraints controlling their origin. Massive Cyprus-type sulphides characterized by relatively high Zn, Se, Au, Mo, Hg, and Sb content are composed of pyrite, chalcopyrite, bornite, and in lesser amounts covellite, siegenite, sphalerite, selenide-clausthalite, telluride-melonite, and occasionally tennantite–tetrahedrite. Massive Fe–Cu–Co–Zn-type sulphides associated with magnetite occur in a matrix of calcite and an unknown (Fe,Mg) silicate, resembling Mg–hisingerite within a deformed/metamorphosed ophiolite zone. The texture and mineralogical characteristics of this sulphide-magnetite ore suggest formation during a multistage evolution of the ophiolite complex. Sulphides (pyrrhotite, chalcopyrite, bornite, and sphalerite) associated with magnetite, at deeper parts of the Pindos (Tsoumes), exhibit relatively high Cu/(Cu + Ni) and Pt/(Pt + Pd), and low Ni/Co ratios, suggesting either no magmatic origin or a complete transformation of a preexisting magmatic assemblages. Differences recorded in the geochemical characteristics, such as higher Zn, Se, Mo, Au, Ag, Hg, and Sb and lower Ni contents in the Pindos compared to the Othrys sulphides, may reflect inheritance of a primary magmatic signature. Full article

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. Full article

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. Full article

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. Full article

Symplectites comprising clausthalite (PbSe) and host Cu-(Fe)-sulphides (chalcocite, bornite, and chalcopyrite) are instructive for constraining the genesis of Cu-Au-(U) ores if adequately addressed at the nanoscale. The present study is carried out on samples representative of all three Cu-(Fe)-sulphides displaying clausthalite inclusions that vary in size, from a few µm down to the nm-scale (<5 nm), as well as in morphology and inclusion density. A Transmission Electron Microscopy (TEM) study was undertaken on foils prepared by Focussed Ion Beam and included atom-scale High-Angle Annular Dark-Field Scanning TEM (HAADF-STEM) imaging. Emphasis is placed on phase relationships and their changes in speciation during cooling, as well as on boundaries between inclusions and host sulphide. Three species from the chalcocite group (Cu_2–xS) are identified as 6a digenite superstructure, monoclinic chalcocite, and djurleite. Bornite is represented by superstructures, of which 2a and 4a are discussed here, placing constraints for ore formation at T > 265 °C. A minimum temperature of 165 °C is considered for clausthalite-bearing symplectites from the relationships with antiphase boundaries in 6a digenite. The results show that alongside rods, blebs, and needle-like grains of clausthalite within the chalcocite that likely formed via exsolution, a second, overprinting set of replacement textures, extending down to the nanoscale, occurs and affects the primary symplectites. In addition, other reactions between pre-existing Se, present in solid solution within the Cu-(Fe)-sulphides, and Pb, transported within a fluid phase, account for the formation of composite, commonly pore-attached PbSe and Bi-bearing nanoparticles within the chalcopyrite. The inferred reorganisation of PbSe nanoparticles into larger tetragonal superlattices represents a link between the solid solution and the symplectite formation and represents the first such example in natural materials. Epitaxial growth between clausthalite and monazite is further evidence for the interaction between pre-existing Cu ores and fluids carrying REE, P, and most likely Pb. In U-bearing ores, such Pb can form via decay of uranium within the ore, implying hydrothermal activity after the initial ore deposition. The U-Pb ages obtained for such ores therefore need to be carefully assessed as to whether they represent primary ore deposition or, more likely, an overprinting event. A latest phase of fluid infiltration is the recognised formation of Cu-selenide bellidoite (Cu₂Se), as well as Fe oxides. Full article