Search Results (29)

Zoharite (IMA 2017-049), (Ba,K)₆ (Fe,Cu,Ni)₂₅S₂₇, and gmalimite (IMA 2019-007), ideally K₆□Fe²⁺₂₄S₂₇, are two new sulfides of the djerfisherite group. They were discovered in an unusual gehlenite–wollastonite paralava with pyrrhotite nodules located in the Hatrurim pyrometamorphic complex, Negev Desert, Israel. Zoharite and gmalimite build grained aggregates confined to the peripheric parts of pyrrhotite nodules, where they associate with pentlandite, chalcopyrite, chalcocite, digenite, covellite, millerite, heazlewoodite, pyrite and rudashevskyite. The occurrence and associated minerals indicate that zoharite and gmalimite were formed at temperatures below 800 °C, when sulfides formed on external zones of the nodules have been reacting with residual silicate melt (paralava) locally enriched in Ba and K. Macroscopically, both minerals are bronze in color and have a dark-gray streak and metallic luster. They are brittle and have a conchoidal fracture. In reflected light, both minerals are optically isotropic and exhibit gray color with an olive tinge. The reflectance values for zoharite and gmalimite, respectively, at the standard COM wavelengths are: 22.2% and 21.5% at 470 nm, 25.1% and 24.6% at 546 nm, 26.3% and 25.9% at 589 nm, as well as 27.7% and 26.3% at 650 nm. The average hardness for zoharite and for gmalimite is approximately 3.5 of the Mohs hardness. Both minerals are isostructural with owensite, (Ba,Pb)₆(Cu,Fe,Ni)₂₅S₂₇. They crystallize in cubic space group Pm$\overline{3}$m with the unit-cell parameters a = 10.3137(1) Å for zoharite and a = 10.3486(1) Å for gmalimite. The calculated densities are 4.49 g·cm⁻³ for the zoharite and 3.79 g·cm⁻³ for the gmalimite. The primary structural units of these minerals are M₈S₁₄ clusters, composed of MS₄ tetrahedra surrounding a central MS₆ octahedron. The M site is occupied by transition metals such as Fe, Cu, and Ni. These clusters are further connected via the edges of the MS₄ tetrahedra, forming a close-packed cubic framework. The channels within this framework are filled by anion-centered polyhedra: SBa₉ in zoharite and SK₉ in gmalimite, respectively. In the M₈S₁₄ clusters, the M atoms are positioned so closely that their d orbitals can overlap, allowing the formation of metal–metal bonds. As a result, the transition metals in these clusters often adopt electron configurations that reflect additional electron density from their local bonding environment, similar to what is observed in pentlandite. Due to the presence of shared electrons in these metal–metal bonds, assigning fixed oxidation states—such as Fe²⁺/Fe³⁺ or Cu⁺/Cu²⁺—becomes challenging. Moreover, modeling the distribution of mixed-valence cations (Fe²⁺/³⁺, Cu⁺/²⁺, and Ni²⁺) across the two distinct M sites—one located in the MS₆ octahedron and the other in the MS₄ tetrahedra—often results in ambiguous outcomes. Consequently, it is difficult to define an idealized end-member formula for these minerals. Full article

In this paper, we present a one-step low-temperature solution combustion synthesis (SCS) of CuS nanoparticulated functional films processed via a simple blade-coating technique. This SCS route uses thiourea as a fuel and sulfur source, combined with copper(II) nitrate as an oxidant and a cupric ion source in an aprotic solvent such as non-toxic DMSO. It is hereby shown that the proposed SCS process formed a stable and completely dissolved molecular ink of thiourea and copper ion complexes, crucial for obtaining the pure crystalline phase of CuS nanoparticles (NPs). The CuS was formed by calcination at a low temperature of 200 °C during a brief annealing time of 20 min, to promote the synthesis of ~10 nm CuS NPs. The obtained CuS NPs were thoroughly analyzed in terms of structure and optoelectronic properties using various analytic and spectroscopic techniques, including TGA, XRD, FE-SEM, EDS, AFM, and four-point probe electrical resistivity measurements. The functionality of the prepared CuS nanoparticulated interlayers was evaluated by incorporating them as a hole injection layer (HIL) in Super Yellow (SY) organic light-emitting diodes (OLEDs). Full article

The Imourkhssen porphyry Cu±Mo±Au±Ag deposit is located at the Ouzellagh-Siroua Salient (OSS) straddling the boundary between the central Anti-Atlas and the central High Atlas. It is characterized by a typical porphyry-style mineralization. The volcanic rocks are intruded by numerous magmatic rocks of the Ouarzazate Group (580–539 Ma), referred to as the Late Ediacaran magmatic suites (LEMS). Of these, the Askaoun, Imourkhssen, and Imourgane granites are the most significant as they are related to the porphyry mineralization. The entire set is intruded by the Zaghar mafic dyke swarms. Zircon U-Pb dating of the Imourkhssen granite and the ore-bearing granite porphyry shows that these intrusive rocks were emplaced at 558 ± 1 and 550 ± 2 Ma, respectively. Moreover, the whole-rock major and trace element geochemistry reveal a high-K calc-alkaline I-type composition, consistent with an emplacement in a post-collisional setting under a trans-tensional tectonic regime. Ore bodies are hosted by the Askaoun granodiorite as well as the Imourgane granite. The mineralization occurs as fine-grained dissemination and infills of hydrothermally altered NNE–SSW to N–S trending veins and veinlets. Ore-related hydrothermal alteration consists of potassic, chlorite-sericite, serecitic, and propylitic mineral assemblages along with pervasive silicification and pyritization, providing a porphyry-style alteration pattern. The ore periods comprise supergene and magmatic-hydrothermal periods. The latter includes primary dissemination and secondary NNE–SSW to N–S ore-bearing system stages. The occurrence of molybdenite is either restricted to the potassic and chlorite-sericite alteration zones of the ore-bearing granite as fine disseminations or alternatively as veinlet infills within the propylitic halos. The molybdenite occurrences along with pyrite, chalcopyrite, galena, and tennantite dissemination are assigned to the primary ore stage, while the NNE–SSW to N–S ore-bearing system is related to the secondary ore stage. It consists of pyrite, chalcopyrite, bornite, covellite, diagenite, sphalerite, hematite, galena, gold, and chenguodaite. The predominance of cockade and crack-and-seal textures suggest multiple episodes of ore-forming fluid circulations under epithermal conditions. The supergene stage is achieved by subordinate malachite, azurite, barite, hematite, epsomite, and chrysocolla. From the descriptions above, we argue that the Imourkhssen Cu±Mo±Au±Ag mineralization shares many mineralogical and paragenetic attributes of porphyry-copper deposits. Full article

Heterogeneous grains in the heavy fractions of the placers of the Olkhovaya-1 river (Kamchatka Cape Peninsula, Eastern Kamchatka, Russia) containing Au-Ag, Au-Cu, and Au-Ag-Cu particles were analyzed using scanning electron microscopy, electron-probe microanalysis, and X-ray powder diffractometry. The analyses showed that auricupride dominates in some grains, whereas in others, the main phases are tetra-auricupride or Ag-rich and (or) Au-rich alloys. It was revealed that in the central parts of some grains of exsolution structures, auricupride Cu_3.04–2.74Au_0.96–1.26 (Ag < 1 wt.%) occurs in intergrowths with low-fineness Ag_0.86–0.67Au_0.09–0.33Cu_<0.05 solid solutions (160‰–480‰), and tetra-auricupride Cu_1.12–0.87Au_0.88–1.11Ag_<0.02 (Ag < 2 wt.%) occurs with higher-fineness Au_0.73–0.62Ag_0.2–0.38Cu_<0.07 solid solutions (520‰–850‰). We also observed, mainly in the peripheral parts of the grains, insignificant amounts of secondary phases that were compositionally similar to Cu₂Au, Cu₃Au₂, Au₃Cu₂, Au₂Cu, Au₃Cu, high-fineness gold with impurities of Cu and occasionally Ag (>850‰), and pure gold. In intergrowths with auricupride and tetra-auricupride, we also observed earlier-formed silicates (garnet, pyroxene, chlorite, epidote, titanite), syngenetic sulfides (pyrrhotite, bornite, galena), and later minerals (chalcocite, covellite, anilite, cuprite, goethite, etc.). The XRD analysis of the peripheral parts of some grains showed the presence of auricupride (Cu₃Au), tetra-auricupride CuAu (I) and Cu(Au_0.92Ag_0.08) (II), and gold. The profiles show the absence of peaks of the Au₃Cu phase and other Au-Ag-Cu phases identified by the EMPA, which is likely due to their low concentrations in the samples or their structural similarity to gold. It is assumed that the probable source of Au-Ag-Cu mineralization in the Olkhovaya-1 river placers is located in the upper reaches of watercourses that erode the ultrabasic massif of Mounts Soldatskaya and Golaya (Kamchatka Cape Peninsula). Full article

The current study sought to investigate the physiochemical conditions and fluid evolution within the Yolindi Cu-Fe skarn mineralization located in the Biga Peninsula, NW Turkey. This was accomplished through a comprehensive investigation of geological and mineralogical data, along with isotopic analyses of sulfur (δ³⁴S), carbon (δ¹³C), and oxygen (δ¹⁸O) of sulfide and calcite minerals, respectively, as well as fluid inclusion data pertaining to various minerals (e.g., andradite, quartz, and calcite). The Yolindi area features a complex geological framework, including the Paleozoic Kalabak Group (which includes the Torasan, Yolindi, and Sazak formations) and the Triassic Karakaya Complex. These formations were subsequently intruded via Early Miocene Şaroluk granitoids and Hallaçlar volcanics. Skarn formation is zoned into endoskarn and exoskarn types (being categorized into proximal, intermediate, and distal zones), with distinct mineral assemblages indicating concentric and contact metamorphic alteration patterns around the western part of Şaroluk granitoid intrusion in contact with the Torasan formation. The ore mineralogy and paragenesis suggest three distinct stages of evolution: an initial phase of prograde metasomatism characterized by the formation of magnetite and pyrite alongside anhydrous calc-silicate minerals; a subsequent phase of retrograde alteration marked by the formation of epidote, actinolite, and scapolite, accompanied by the occurrence of chalcopyrite and specular hematite; and finally, a post-metasomatic stage involving oxidation processes that led to the development of secondary mineral assemblages containing cerussite, covellite, and malachite. Sulfur isotopes (δ³⁴S) of sulfides from endoskarn (from +0.27 to +0.57‰_VCDT) to intermediate exoskarn (from −9.44 to −5.46‰_VCDT) zones indicate a diverse sulfur source, including magmatic, sedimentary, and possibly organic matter. δ³⁴S values in hydrothermal fluids suggest a magmatic–hydrothermal origin, with endoskarn and proximal zone fluids showing a slight negative signature and intermediate zone fluids indicating a strong influence from organic-rich or metamorphic sulfur reservoirs. Carbon and oxygen isotopic compositions (δ¹³C and δ¹⁸O) of calcite revealed a progression from marine carbonate signatures in marble samples (from +1.89 to +2.23‰_VPDB; from +21.61 to +21.73‰_VSMOW) to depleted values in prograde (from −6.0 to +0.09‰_VPDB; from +6.22 to +18.14‰_VSMOW) and retrograde skarns (from −3.8 to −2.25‰_VPDB; from +0.94 to +3.62‰_VSMOW), reflecting interactions with high-temperature magmatic fluids and meteoric water mixing. The fluid inclusions in prograde minerals generated under the conditions of fluid boiling exhibited high temperatures, reaching up to 412 °C, and salinities up to 26 wt.% NaCl equivalent. Conversely, the fluid inclusions in retrograde minerals, which were generated due to fluid mixing, exhibited lower temperatures (with an average of 318 °C) and salinities with an average of 4.9 wt.% NaCl equivalent. This indicated that the cooler and more diluted fluids mix with meteoric waters and interact with organic materials in the host rocks. This suggests a multifaceted origin involving various sources and processes. Therefore, this study concluded that the skarn mineralization in the Yolindi area resulted from complex interactions between magmatic, metamorphic, and meteoric fluids, reflecting a dynamic ore-forming environment with implications for the regional metallogeny of Cu-Fe skarn deposits. Full article

In this study, chemical leaching, XRD, SEM, and XPS analyses were conducted to investigate the dissolution and passivation mechanisms of chalcopyrite under pressurized oxidative conditions in water. The chemical leaching results showed that the chalcopyrite could be dissolved by pressurized leaching without any acid addition, i.e., in an O₂–H₂O system, and the copper leaching rate reached 96.4% under the optimal conditions of 180 °C, 1.5 MPa, 900 rpm, and 90 min. The XRD, SEM, and XPS data suggested that a large proportion of the chalcopyrite dissolved in solution via the mineral phase transformation of CuFeS₂→Cu²⁺ and CuFeS₂→CuS→Cu²⁺, i.e., some of the chalcopyrite directly leached into solution as Cu²⁺, and some of it was first converted to CuS and then to Cu²⁺. The primary passivation layers during the chalcopyrite pressurized water leaching were hematite, pyrite, and covellite; however, none of them covered the un-leached mineral surface or inhibited chalcopyrite dissolution, as long as the agitation speed and leaching time were maintained over 700 rpm and 60 min, respectively. Finally, a model of chalcopyrite’s dissolution and passivation mechanism during pressurized water leaching was proposed. Full article

The studied copper ore deposit is located in Miedzianka Mountain (Świętokrzyskie Mountains, central Poland). This deposit was exploited from the 13th century to the 1950s; therefore numerous historical adits are currently present. One of these is Teresa adit (established in 1805), consisting of underground mining corridors and natural cave developed in the Upper Devonian limestones, partially transformed by mining works. Samples of copper- and rock-forming minerals in limestones collected at seven sites within the richest copper-bearing mineralisation in this adit were studied with petrographic investigation of thin sections, micro-area chemical analysis (EDS), and XRD. This study shows the presence of various minerals: (a) Cu-Fe sulphides (relics of chalcopyrite) and Cu sulphides (covellite, chalcocite), (b) Cu-Fe oxides (cuprite and hematite), (c) Ca and Cu carbonates (calcite, azurite, and malachite), (d) clay minerals (Fe-Mg illite), and (e) micro-crystalline silica (quartz). For the first time in the studied deposit, we described chalcopyrite relics in cuprite pseudomorphosis, hematite with admixture of vanadium in pinkish-creme veins in limestones, and the presence of an admixture of Fe-Mg illite and microcystaline silica within cracks of limestones. In addition, for the first time, unit cell parameters of malachite and azurite from Miedzianka Mountain were determined, indicating very low substitutions of atoms other than Cu in their structures. We suppose that the minerals studied were formed during three types of copper mineralisation processes: (a) hydrothermal (relics of chalcopyrite), (b) secondary weathering (chalcocite, covellite, cuprite, hematite), and (c) adsorptive mineralisation (azurite, malachite). The latter stage is related to residuum, which consists of a mixture of Fe-Mg illite and micro-crystalline quartz, which was formed during the dissolution of limestones in karst processes in some crevices. We proposed a model of the formation of copper carbonates in the adsorption stage of the copper-bearing mineralisation in Miedzianka Mountain deposits. Two generations of calcite veins (older—red calcite and younger—crème-pinkish calcite) were also detected. Mineralogical–petrographical studies of samples revealed a high scientific and educational value. Due to the fact that the Teresa adit is planned to be made available to geotourists, this work is worth presenting to the public either in the adit and/or in a local museum in Miedzianka village. Full article

The search for effective reagents for the flotation of non-ferrous metals from mineral raw materials is an actual problem. The article discusses the results of research on improving the technology of processing copper–molybdenum ores using a combined collector emulsion. The object of research was copper–molybdenum ore containing 0.43% copper and 0.0089% molybdenum. Copper minerals are represented by chalcopyrite 1.2% and chalcocite 0.015%, while covellite is present in a much smaller amount. The main mineral of molybdenum is molybdenite. The cycle of collective copper–molybdenum flotation includes the main flotation, control flotation, and three re-cleanings of concentrate. In the basic mode, the collective Cu–Mo concentrate was produced with the copper content of 16.25% with an extraction of 77.79% and with the molybdenum content of 0.45% with an extraction of 79.38%. Reaflot, thionocarbamate, and butyl xanthate were used in a ratio of 1:3:15 to prepare a combined collector agent. In order to produce the combined collector emulsion, the best degree of dispersion, which amounted to 99.5% of particles with a size of −3.6 μm, was chosen. During the Cu–Mo ore flotation using an optimally dispersed microemulsion of the combined collector agent, a collective Cu–Mo concentrate was obtained with a copper content of 18.2% with an extraction of 83.58%, and with a molybdenum content of 0.49% with an extraction of 88.46%. The use of a combined collector agent increases the extraction of copper into the collective Cu–Mo concentrate by 5.79%, while the extraction of molybdenum increases by 9.08%. Full article

The direct or indirect discharge of toxic and non-biodegradable organic pollutants into water represents a huge threat that affects human health and the environment. Therefore, the treatment of wastewater, using sustainable technologies, is absolutely necessary for reusability. Photocatalysis is considered one of the most innovative advanced techniques used for pollutant removal from wastewater, due to its high efficiency, ease of process, low-cost, and the environmentally friendly secondary compounds that occur. The key of photocatalysis technology is the careful selection of catalysts, usually semiconductor materials with high absorption capacity for solar light, and conductivity for photogenerated charge carriers. Among copper sulfides, CuS (covellite), a semiconductor with different morphologies and bandgap values, is recognized as an important photocatalyst used for the removal of organic pollutants (dyes, pesticides, pharmaceutics etc.) from wastewater. This review deals with recent developments in organic pollutant photodegradation, using as catalysts various CuS nanostructures, consisting of CuS NPs, CuS QDs, and heterojunctions (CuS/ carbon-based materials, CuS/organic semiconductor, CuS/metal oxide). The effects of different synthesis parameters (Cu:S molar ratios, surfactant concentration etc.) and properties (particle size, morphology, bandgap energy, and surface properties) on the photocatalytic performance of CuS-based catalysts for the degradation of various organic pollutants are extensively discussed. Full article

This study contributes to our understanding of the evolution of Halılar Cu-Pb (±Zn) mineralization (NW Turkey) based on mineralogical and geochemical results and sulfur isotope data. The study area represents local Cu-Pb with some Zn brecciated-stockwork vein type mineralization along the NE–SW fault gouge zone at the lower boundary of the Sakarkaya and Düztarla granitoid rocks. Two main zones, consisting of sericite–quartz–chlorite ± kaolinite ± pyrite (i.e., zone-1) and calcite–epidote–albite ± chlorite ± sericite (i.e., zone-2), were observed within the central ore mineral zone at the mining site. Different mineralization assemblages were recorded; the main ore mineral contains chalcopyrite, galena, pyrite, and sphalerite within alteration zone-1, and the oxidation/supergene mineralization includes covellite and goethite. The mass balance calculations show that the samples of zone-1 show an increase in SiO₂, Fe₂O₃, K₂O, and LOI along with Ag, As, Cu, Mo, Pb, S, Sb, and Zn, reflecting high pyritization with sericitization and silicification. On the other hand, the samples from zone-2 are rich in CaO; Na₂O; P₂O₅; TiO₂; LOI; and carbon-reflecting calcite, epidote, and albite alterations. A uniform magmatic sulfur source of Halılar sulfides is suggested by their mean δ³⁴S value of −1.62‰. Furthermore, the primary metal source is metasediments and intrusive Düztarla granitoid magmatism. These observations suggest that the Halılar metasediment-hosted Cu-Pb (±Zn) mineralization was formed by epigenetic hydrothermal processes after sedimentation/diagenesis and metamorphism. Full article

Chalcocite is the most abundant secondary copper sulfide globally, with the highest copper content, and is easily treated by conventional hydrometallurgical processes, making it a very profitable mineral for extraction. Among the various leaching processes to treat chalcocite, chloride media show better results and have a greater industrial boom. Chalcocite dissolution is a two-stage process, the second being much slower than the first. During the second stage, in the first instance, it is possible to oxidize the covellite in a wide range of chloride concentrations or redox potentials (up to 75% extraction of Cu). Subsequently, CuS₂ is formed, which is to be oxidized. It is necessary to work at high concentrations of chloride (>2.5 mol/L) and/or increase the temperature to reach a redox potential of over 650 mV, which in turn decreases the thickness of the elemental sulfur layer on the mineral surface, facilitating chloride ions to generate a better porosity of this. Finally, it is concluded that the most optimal way to extract copper from chalcocite is, during the first stage, to work with high concentrations of chloride (50–100 g/L) and low concentrations of sulfuric acid (0.5 mol/L) at a temperature environment, as other variables become irrelevant during this stage if the concentration of chloride ions in the system is high. While in the second stage, it is necessary to increase the temperature of the system (moderate temperatures) or incorporate a high concentration of some oxidizing agent to avoid the passivation of the mineral. Full article

We report the effect of thermolysis time on the morphological and optical properties of CuS nanoparticles prepared from Cu(II) dithiocarbamate single-source precursor. The as-prepared copper sulfide nanoparticles were used as photocatalysts for the degradation of crystal violet (CV), methylene blue (MB), rhodamine B (RhB), and a ternary mixture of the three dyes (CV/MB/RhB). Powder XRD patterns confirmed the hexagonal covellite phase for the CuS nanoparticles. At the same time, HRTEM images revealed mixed shapes with a particle size of 31.47 nm for CuS1 prepared at 30 min while CuS2 prepared at 1 h consists of mixtures of hexagonal and nanorods shaped particles with an average size of 21.59 nm. Mixed hexagonal and spherically shaped particles with a size of 17.77 nm were obtained for CuS3 prepared at 2 h. The optical bandgaps of the nanoparticles are 3.00 eV for CuS1, 3.26 eV for CuS2 and 3.13 eV for CuS3. The photocatalytic degradation efficiency showed that CuS3 with the smallest particle size is the most efficient photocatalyst and degraded 85% of CV, 100% of MB, and 81% of RhB. The as-prepared CuS showed good stability and recyclability and also degraded ternary dyes mixture (CV/MB/RhB) effectively. The byproducts of the dye degradation were evaluated using ESI-mass spectrometry. Full article

Pure-phase Cu_2−xS (x = 1, 0.2) nanoparticles have been synthesized by the thermal decomposition of copper(II) dithiocarbamate as a single-source precursor in oleylamine as a capping agent. The compositions of the Cu_2−xS nanocrystals varied from CuS (covellite) through the mixture of phases (CuS and Cu_7.2S₄) to Cu₉S₅ (digenite) by simply varying the temperature of synthesis. The crystallinity and morphology of the copper sulfides were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), which showed pure phases at low (120 °C) and high (220 °C) temperatures and a mixture of phases at intermediate temperatures (150 and 180 °C). Covellite was of a spherical morphology, while digenite was rod shaped. The optical properties of these nanocrystals were characterized by UV−vis–NIR and photoluminescence spectroscopies. Both samples had very similar absorption spectra but distinguishable fluorescence properties and exhibited a blue shift in their band gap energies compared to bulk Cu_2−xS. The pure phases were used as catalysts for the photocatalytic degradation of tetracycline (TC) under visible-light irradiation. The results demonstrated that the photocatalytic activity of the digenite phase exhibited higher catalytic degradation of 98.5% compared to the covellite phase, which showed 88% degradation within the 120 min reaction time using 80 mg of the catalysts. The higher degradation efficiency achieved with the digenite phase was attributed to its higher absorption of the visible light compared to covellite. Full article

The ore deposits of Bou Caïd (Ouarsenis, Algeria) occur in Jurassic and Cretaceous sedimentary rocks. The barite and Pb-Zn (Fe, Cu, and F) ore deposits of Bou Caïd belong to vein- and karst-type. The mineralization is represented in the whole area by a mixture of barite (currently still exploited) and nonsulfides consisting of hemimorphite, smithsonite, cerussite, hydrozincite, and Fe-oxy-hydroxides, with remnants of galena and sphalerite in variable proportions. Mineralogical and geochemical analyses were carried out on the Bou Caïd nonsulfides. Several samples representing nonsulfide mineralization (Grand Pic and at Srâa Abdelkader) were subjected to a multidisciplinary analytical approach, using optical microscopy (OM), powder X-ray diffraction (PXRD), Scanning Electron Microscopy with Energy Dispersive Spectrometry (SEM-EDS). Nonsulfide mineralization consists of a mixture of hemimorphite, hydrozincite, smithsonite, cerussite, and Fe-oxy-hydroxides, often with zebra-like textures. In the proposed paragenetic scheme, covellite and chalcocite are followed by cerussite, jarosite, smithsonite, and hydrozincite. Then, hemimorphite crystallizes, accompanied by mimetite, traces of malachite and clay minerals (also Zn-bearing), precipitate. Fe-(Mn)-oxy-hydroxides can form during various phases of the supergene stage. Small amounts of late barite can be related to partial remobilization and occur as reprecipitation products. Stable isotope analyses were performed on the calcites and metal carbonates of the supergene ores. Carbon and oxygen isotope values of smithsonite and hydrozincite were comparable to published supergene Zn carbonate data. The isotope values of the Bou Caïd calcites fell both into the hydrothermal carbonate and in the supergene fields. 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