Surface potential and dixanthogen stability on chalcopyrite surface

Contact angle measurements, ultraviolet (UV) spectroscopy and voltammetry were used in this investigation to study the effect of various externally applied potentials on the stability of dixanthogen at synthetic and natural chalcopyrite surfaces.The results of contact angle measurements indicate that synthetic and natural chalcopyrites have similar wettabilities. Their hydrophobic potential range in a 7 × 10^− 4 M PAX solution was + 0.04 V to + 0.44 V vs. NHE at pH 10 and was − 0.01 V to + 0.54 V at pH 7.UV spectroscopic results show that dixanthogen began to form on the chalcopyrite surface at a potential of + 0.04 V vs. NHE at pH 10 and − 0.01 V vs. NHE at pH 7. The amount of dixanthogen formed on the chalcopyrite surface initially increased with the increase of the applied potential and then decreased with the increasing potential. The optimum potential range for dixanthogen formation on the chalcopyrite surface was from + 0.14 V to + 0.34 V vs. NHE at pH 10 and from + 0.14 V to + 0.44 V vs. NHE at pH 7. It was difficult to completely remove the dixanthogen film on the chalcopyrite surface.     

Ore minerals down to the nanoscale: Cu-(Fe)-sulphides from the iron oxide copper gold deposit at Olympic Dam,South Australia

Cu-Fe-sulphide mineral assemblages from the Olympic Dam (OD) Fe-oxide Cu-U-Au-Ag deposit, South Australia, are studied down to the nanoscale to explore the potential these minerals have for understanding genetic processes such as primary deposit zonation. Cu-Fe-sulphide pairs: ‘brown’ bornite associated with chalcopyrite (bornite-chalcopyrite zone); and symplectites of ‘purple’ bornite with species from the chalcocite group, Cu_2 − xS (bornite-chalcocite zone), co-define an upwards and inwards deposit-scale zonation at OD. In the bornite-chalcocite zone, there is also an increase in the proportion of chalcocite relative to bornite within the symplectites towards upper levels. In this case, two-phase Cu_2 − xS assemblages are also present, as anisotropic, hexagonal chalcocite (CcH) with lamellar exsolutions of digenite, distinguishable at the μm-scale. Using compositional data (electron microprobe) combined with Transmission Electron Microscopy (TEM) study of foils prepared in–situ via Focused Ion Beam (FIB)-SEM, we show that Cu-Fe-sulphides from different ore zones feature nanoscale intergrowths, lattice defects, superstructure domains (na) and antiphase boundary domains (APBs) that can be interpreted as due to exsolution, coarsening and phase transformation during cooling from high-T solid solutions in the system Cu-Fe-S and sub-systems according to published phase diagrams. ‘Brown’ bornite [(Cu + Fe)/S > 5] contains pervasive lamellae of chalcopyrite which extend down to the nanoscale; such specimens appear homogeneous at the μm-scale. ‘Purple bornite’ [(Cu + Fe)/S < 5] in high-bornite symplectites is associated with chalcocite that shows APBs with 6a digenite and low-T chalcocite. Comparable APBs are also found in the ‘chalcocite’ zone with apparent homogeneity at the μm-scale. Both bornites contain exsolutions of djurleite. Systematic variation of Me/S and Cu/Fe in the two types of bornite points, however, to distinct origins from different bornite solid-solutions in the system Cu-Fe-S. Both show 2a and 4a intermediate superstructures. High-order superstructures (6a and incommensurate na) are restricted to the ‘purple’ bornite whereas the 2a4a low-T superstructure is found in both cases. Me/S ratios in the chalcocite group are variable; lower ratios (down to 1.8; digenite) are more common in chalcocite from symplectites with ‘purple’ bornite. Me/S can be as low as 1.4 where associated with ‘blue’ varieties (‘blaubleibender covellin’) of replacement origin. The two-phase Cu_2 − xS associations contain hexagonal chalcocite (Me/S = 1.95), lamellae of Cu-rich digenite (Me/S = 1.92), and anilite (Cu₇S₄) as nm-scale lamellae. Digenite shows 3a and 6a superstructures and CcH shows transition to pseudo-orthorhombic chalcocite. The presence of superstructures, high-T species and APBs is evidence for Cu-(Fe)-sulphide formation from high-T solid solutions at T > 300 °C (high-T phases, Cu-poor digenite), followed by cooling along distinct paths down to < 120 °C (APBs). The scenario of ‘exsolution from primary solid-solution’, corroborated by the consistency in phase relations within each zone across different scales of observation from deposit scale to nanoscale, backs up a model of primary hypogene ore precipitation rather than replacement, and accounts for the observed vertical zoning at OD. The FIB-TEM approach here is readily applicable to other deposits and shows that nanoscale observations are a valuable, although often overlooked, source of information to constrain ore genesis.     

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.     

The oxidation states of copper and iron in mineral sulfides, and the oxides formed on initial exposure of chalcopyrite and bornite to air

Metal L_2,3, sulfur K and oxygen K near-edge X-ray absorption fine structure (NEXAFS) spectra for chalcopyrite, bornite, chalcocite, covellite, pyrrhotite and pyrite have been determined from single-piece natural mineral specimens in order to assess claims that chalcopyrite should be regarded as Cu^IIFe^IIS₂ rather than Cu^IFe^IIIS₂, and that copper oxide species are the principal initial oxidation products on chalcopyrite and bornite exposed to air. Spectra were obtained using both fluorescence and electron yields to obtain information representative of the bulk as well as the surface. Where appropriate, NEXAFS spectra have been interpreted by comparison with the densities of unfilled states and simulated spectra derived from ab initio calculations using primarily the FEFF8 code and to a lesser extent WIEN2k. Metal 2p and S 2p photoelectron spectra excited by monochromatised Al K_α X-rays were determined for each of the surfaces characterised by NEXAFS spectroscopy. The X-ray excited Cu LMM Auger spectrum was also determined for each copper-containing sulfide. FEFF8 calculations were able to simulate the experimental NEXAFS spectra quite well in most cases. For covellite and chalcocite, it was found that FEFF8 did not provide a good simulation of the Cu L₃-edge spectra, but WIEN2k simulations were in close agreement with the experimental spectra. Largely on the basis of these simulations, it was concluded that there was no convincing evidence for chalcopyrite to be represented as Cu^IIFe^IIS₂, and no strong argument for some of the Cu in either bornite or covellite to be regarded as Cu(II). The ab initio calculations for chalcopyrite and bornite indicated that the density of Cu d-states immediately above the Fermi level was sufficient to account for the Cu L₃-edge absorption spectrum, however these incompletely filled Cu d-states should not be interpreted as indicating some Cu(II) in the sulfide structure. It was also concluded that the X-ray absorption spectra were quite consistent with the initial oxidation products on chalcopyrite and bornite surfaces being iron oxide species, and inconsistent with the concomitant formation of copper-oxygen species.     

Experimental replacement of chalcopyrite by bornite: Textural and chemical changes during a solid-state process

Chalcopyrite was reacted with covellite and with chalcocite, respectively, between 200°C and 500°C. The ensuing solid-state replacement of chalcopyrite by bornite was studied both texturally and chemically. The relatively oxidizing conditions of the reaction chalcopyrite+covellite result in massive replacement, lacking structural control, where bornite and pyrite form complex intergrowth textures in chalcopyrite. Bornite nucleates around growing pyrite aggregates because of the release of copper and a decrease in volume. Diffusion of sulphur along grain boundaries and fractures largely controls the textural development. Reaction under the relatively reducing conditions involving chalcopyrite+chalcocite results in replacement of chalcopyrite in the sequence where chalcopyrite is replaced by bornite, below about 355°C, and by intermediate solid solution (ISS) and later bornite, above 355°C. The textural development, changing from replacement, apparently uninfluenced by directional properties in the host, to semioriented replacement, is structurally controlled. This suggests that the process is governed by diffusion of copper and iron through a sulphur framework. It is suggested that the observed formation of oriented bornite lamellae in chalcopyrite and in ISS during the chalcopyrite+chalcocite reaction may be explained by replacement exsolution at constant temperature.     

Geochemistry,mineralogy and genesis of the Ayazmant Fe–Cu skarn deposit in Ayvalik, (Balikesir), Turkey

The Ayazmant Fe–Cu skarn deposit is located approximately 20 km SE of Ayval?k or 140 km N of Izmir in western Turkey. The skarn occurs at the contact between metapelites and the metabasites of the Early Triassic K?n?k Formation and the porphyritic hypabyssal intrusive rocks of the Late Oligocene Kozak Intrusive Complex. The major, trace, and rare earth-element geochemical analysis of the igneous rocks indicate that they are I-type, subalkaline, calc-alkaline, metaluminous, I-type products of a high-level magma chamber, generated in a continental arc setting. The ⁴⁰Ar–³⁹Ar isochron age obtained from biotite of hornfels is 20.3 ± 0.1 Ma, probably reflecting the age of metamorphic–bimetasomatic alteration which commenced shortly after intrusion into impure carbonates. Three stages of skarn formation and ore development are recognized: (1) Early skarn stage (Stage I) consisting mainly of garnet with grossular-rich (Gr_75–79) cores and andradite-rich (Gr_36–38) rims, diopside (Di_94–97), scapolite and magnetite; (2) sulfide-rich skarn (Stage II), dominated by chalcopyrite with magnetite, andraditic garnet (Ad₈₄–₈₉), diopside (Di₆₅–₇₅) and actinolite; and (3) retrograde alteration (Stage III) dominated by actinolite, epidote, orthoclase, phlogopite and chlorite in which sulfides are the main ore phases. ⁴⁰Ar–³⁹Ar age data indicate that potassic alteration, synchronous or postdating magnetite–pyroxene–amphibole skarn, occurred at 20.0 ± 0.1 Ma. The high pyroxene/garnet ratio, plus the presence of scapolite in calc-silicate and associated ore paragenesis characterized by magnetite (± hematite), chalcopyrite and bornite, suggests that the bulk of the Ayazmant skarns were formed under oxidized conditions. Oxygen isotope compositions of pyroxene, magnetite and garnet of prograde skarn alteration indicate a magmatic fluid with δ¹⁸O values between 5.4 and 9.5‰. On the basis of oxygen isotope data from mineral pairs, the early stage of prograde skarn formation is characterized by pyroxene (Di_94–97)-magnetite assemblage formed at an upper temperature limit of 576 °C. The lower temperature limit for magnetite precipitation is estimated below 300 °C, on the basis of magnetite–calcite pairs either as fracture-fillings or massive ore in recrystallized limestone-marble. The sulfide assemblage is dominated by chalcopyrite with subordinate molybdenite, pyrite, cubanite, bornite, pyrrhotite, galena, sphalerite and idaite. Gold–copper mineralization formed adjacent to andradite-dominated skarn which occurs in close proximity to the intrusion contacts. Native gold and electrum are most abundant in sulfides, as fine-grained inclusions; grain size with varying from 5 to 20 µm. Sulfur isotope compositions obtained from pyrrhotite, pyrite, chalcopyrite, sphalerite and galena form a narrow range between ? 4.8 and 1.6‰, suggesting the sulfur was probably mantle-derived or leached from magmatic rocks. Geochemical data from Ayazmant shows that Cu is strongly associated with Au, Bi, Te, Se, Cd, Zn, Pb, Ni and Co. The Ayazmant mineralizing system possesses all the ingredients of a skarn system either cogenetic with, or formed prior to a porphyry Cu(Au–Mo) system. The results of this study indicate that the Aegean Region of Turkey has considerable exploration potential for both porphyry-related skarns and porphyry Cu and Au mineralization.     

Leaching of metals from copper smelter flue dust (Mufulira,Zambian Copperbelt)

The leaching behaviour of electrostatic precipitator dust from the Mufulira Cu smelter (Copperbelt, Zambia) was studied using a 48-h pH-static leaching experiment (CEN/TS 14997). The release of metals (Cd, Co, Cu, Ni, Pb and Zn) and changes in mineralogical composition using X-ray diffraction and PHREEQC-2 modelling were investigated in the pH range of 3–7. The highest concentrations of metals were released at pH 3–4.5, which encompasses the natural pH of the dust suspension (～4.3). About 40% of the total Cu was leached at pH 3, yielding 107 g/kg. Chalcanthite (CuSO₄·5H₂O), magnetite (Fe₃O₄) and delafossite (CuFeO₂) represented the principal phases of the studied dust. In contact with water, chalcanthite was dissolved and hydrated Cu sulphates precipitated at pH 4–7. Gypsum (CaSO₄·2H₂O) and secondary Fe or Al phases were observed in the leached residues. Serious environmental impact due to leaching may occur in dust-contaminated soil systems in the vicinity of the smelting plants.     

Rare greenockite (CdS) within the chromite–PGE association in the Bangur Gabbro,Baula-Nuasahi Complex,Eastern India

We report the presence of greenockite from the chromite–PGE–base metal sulfide association in the Bangur Gabbro, Baula-Nuasahi mafic–ultramafic complex. The CdS phase occurs, sans any precursor Cd-bearing phase, as minute grains within siderite micro-veins in close proximity to chlorite in the chalcopyrite + pyrrhotite + pentlandite + violarite assemblage. Using various calibrations, chlorite compositions yielded temperature ranges of 245 to 325 °C. The associated siderite might have formed at or little below the above temperature. Electron probe micro-analyses (EPMA) of greenockite reveal small amounts of Fe (1.01–1.61 wt.%), Zn (1.89–4.54 wt.%), and substitution of Zn for Cd. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of chalcopyrite nearer to and away from siderite micro-veins that host greenockite confirms maximum Cd concentrations of 78 and 144 ppm, respectively, entailing possible derivation of Cd from chalcopyrite. We propose the transport of Cd as bisulfide complex in a low temperature alkaline and reducing fluid and the simultaneous precipitation of greenockite and siderite by reaction with Fe-rich minerals, aided by decrease in pH and/or increase in f_O2.     

Variation of copper isotopes in chalcopyrite from Dabu porphyry Cu-Mo deposit in Tibet and implications for mineral exploration

The study presents copper (Cu) isotope data of mineral separates of chalcopyrite from four drill core samples in the Miocene Dabu porphyry Cu-Mo deposit formed in a post-collisional setting in the Gangdese porphyry copper belt, southern Tibet. Copper isotope values in hypogene chalcopyrite range from –1.48‰ to +1.12‰, displaying a large variation of up to 2.60‰, which demonstrates Cu isotope fractionation at high-temperature during hydrothermal evolution. The majority of measured chalcopyrite isotopic compositions show a gradual increasing trend from –1.48‰ to +1.12‰ with the increase of drilling depth from 130m to 483m, as the alteration assemblages change from potassic to phyllic. Similarly, the other δ⁶⁵Cu values (δ⁶⁵Cu = ((⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_standard − 1) × 1000) of the chalcopyrite show a gradual increasing trend from −1.48‰ to +0.59‰ with the decrease of drilling depth from 130 m to 57 m, as the alteration assemblages change from potassic, phyllic, through argillic to relatively fresh. These observations suggest a genetic link between Cu isotope variation and silicate alteration assemblages formed at different temperatures, indicative of a Rayleigh precipitation process resulting in the large variation of δ⁶⁵Cu values at Dabu. In general, samples closest to the center of hydrothermal system dominated by high-temperature potassic alteration are isotopically lighter, whereas samples dominated by low-temperature phyllic alteration peripheral to the center are isotopically heavier. The predicted flow pathways of hydrothermal fluids are from No. 0 to No. 3 exploration line, and the lightest δ⁶⁵Cu values are the most proximal to the hydrothermal source. Finally, we propose that the northwest side of the No. 0 exploration line has high potential for hosting undiscovered orebodies. The pattern of Cu isotope variation in conjunction with the features of silicate alteration in porphyry system can be used to trace the hydrothermal flow direction and to guide mineral exploration.     

Indium mineralisation in SW England: Host parageneses and mineralogical relations

The SW England ore region contains significant amounts of indium (In) in Early Permian granite-related skarn and lode parageneses and, to a lesser extent, Triassic epithermal “crosscourse” veins. Ore parageneses that predate granite emplacement (Devonian and Lower Carboniferous sedimentary exhalative and vein parageneses) are largely devoid of In. Cadmium (Cd) and gallium (Ga) occur widely in all sulphide-bearing parageneses across the region with sphalerite concentrations locally reaching 1.74 wt% Cd and 1750 ppm Ga.Indium displays a strong affinity to sulphide-bearing magmatic-hydrothermal parageneses. It occurs in silicate-sulphide skarns, polymetallic sulphide lodes and sulphide-bearing portions of greisen-bordered sheeted vein systems and quartz-tourmaline lodes across the region. Magnetite-silicate skarns and quartz-tourmaline lodes that are devoid of sulphide, in contrast, were comparatively unfavourable for In precipitation. The highest In concentrations are found in mineral lodes associated with the Carnmenellis and St Agnes granites, which are the districts that had the highest historical production of Sn. Total In concentrations in these areas locally exceed 430 ppm, while concentrations elsewhere are systematically below 200 ppm.The principal In hosts are chalcopyrite, sphalerite and stannite group minerals with local concentrations within cassiterite and tennantite. Surprisingly, chalcopyrite accounts for the majority of the In budget throughout the region, although concentrations are highest in sphalerite and stannite group minerals. Sphalerite locally contains up to 1.42 wt% In, chalcopyrite has up to 2200 ppm and stannite group minerals up to 6800 ppm. No In was detected in löllingite, arsenopyrite, rutile, haematite, magnetite, tourmaline, biotite, chlorite, galena, bornite, chalcocite or pyrrhotite. Scattered concentrations in pyrite relate to impurities rather than incorporation by solid solution. Roquesite and possibly dzhalindite or native In formed locally where In-bearing chalcopyrite or sphalerite has been replaced by bornite and quartz. The In partitioning between sphalerite and chalcopyrite varies broadly between 1:1 and 10:1.Sporadic In was included in Triassic crosscourse veins as a result of interactions between migrating CaCl₂-rich basinal brines and earlier formed granite-related parageneses. The interactions involved at least two distinct components: 1) Incorporation of clasts of magmatic-hydrothermal veins in crosscourse veins during faulting, and 2) Dissolution and re-precipitation of magmatic-hydrothermal vein minerals in crosscourse fluids. Local concentrations reach 140 ppm In.The magmatic-hydrothermal parageneses in SW England are comparable to the South China Tin Belt, Mount Pleasant, as well as Erzgebirge/Krušné Hory. Magmatic-hydrothermal fluids associated with peraluminous granites have developed a variety of skarn, greisen, lode and veins parageneses by interactions with their host rocks and contained fluids. Crosscourse epithermal mineralisation occurred as In was transported by CaCl₂-rich basinal brines in a similar manner as In-bearing veins in the West Shropshire ore field.     

Synmetamorphic Cu remobilization during the Pan-African orogeny: Microstructural,petrological and geochronological data on the kyanite-micaschists hosting the Cu(–U) Lumwana deposit in the Western Zambian Copperbelt of the Lufilian belt

The Pan-African Lufilian orogenic belt hosts world-class Cu deposits. In the Congolese Copperbelt (DRC), Cu(–Co) deposits, are mostly hosted within evaporitic and siliciclastic Neoproterozoic metasedimentary rocks (Mines Subgroup) and are interpreted as syn- to late-diagenetic deposits. In this paper, we present new data on Cu(–U) deposit hosted in metamorphic rocks of the internal zone of the Lufilian belt known as the Western Zambian Copperbelt in which a primary Cu mineralization is overprinted by a second syn-metamorphic Cu mineralizing event. This mineralizing event is synchronous with the Pan-African metamorphism affecting both the pre-Katanga basement and the Katanga metasedimentary sequence. Cu(–U) occurrences in the Western Zambian Copperbelt are hosted by kyanite-micaschists metamorphosed in the upper amphibolite facies.Mineral inclusions of graphite, micas and sulfides in kyanite porphyroblasts of the Cu-bearing kyanite-micaschists in the Lumwana Cu deposit point to a sedimentary protolith with relics of an inherited Cu stock. Based on petrologic, microstructural and geochronological evidence, we propose that this initial Cu-stock was remobilized during the Pan-African orogeny. Graphite, micas and sulfides preserved in a first generation of kyanite poikiloblasts (Ky₁) define an inherited S_0/1 foliation developed during the prograde part of the P–T path (D₁ deformation-metamorphic stage) reaching HP–MT metamorphic conditions.Remobilization during the retrograde part of the P–T path is evidenced by chalcopyrite–pyrrhotite and chalcopyrite–bornite delineating a steep-dipping S₂ schistosity and by chalcopyrite and bornite delineating a shallow-dipping S₃ schistosity associated with top to the south kinematic criteria. This retrograde path is coeval with ductile deformation in the kyanite field as evidenced by a second generation of synkinematic kyanite porphyroblasts (Ky₂) transposed in the S₃ schistosity (Ky_2–3), and is marked by progressive cooling from ca. 620 °C down to 580 °C (rutile geothermometry). Syn-S_2–3 metamorphic monazite grains yield U–Th–Pb ages ranging from ca. 540 to 500 Ma.Final retrogression and remobilization of Cu is marked by recrystallization of the sulfides in top to the north C₃ shear bands associated with rutile crystals yielding temperatures from ca. 610 to 540 °C. This final remobilization is younger than ca. 500 Ma (youngest U–Th–Pb age on syn-S₃ recrystallized monazite). These data are consistent with successive Cu remobilization for more than 40 Ma during Pan-African reworking of sediment-hosted deposits either from the basement of the Katanga sedimentary sequence or from the Katanga sequence itself marked by burial (D₁), syn-orogenic exhumation (D₂), and post-orogenic exhumation during gravitational collapse (D₃).     

Bonanza-grade accumulations of gold tellurides in the Early Cretaceous Sandaowanzi deposit,northeast China

The Sandaowanzi epithermal gold deposit (0.5 Moz or ca. 14 tons), located at the northern edge of the Great Xing'an range, NE China, is unique in that nearly all the gold (> 95%) is contained in gold tellurides mostly in bonanza grade ore shoots (the highest grade being up to 20,000 g/t). The bonanza ores are hosted in the central parts of large-scale (> 3 m wide, 200 m long) quartz veins which crosscut Early Cretaceous andesitic trachyte and trachytic andesite, and are, in turn, crosscut by diabase dykes of similar age. There are two ore types: low-grade disseminated ores and high-grade vein ores. In the former, very fine grains of Ag-rich tellurides (mainly hessite and petzite) coexist with sulfides (pyrite, sphalerite, galena and chalcopyrite), occurring as disseminated grains or sometimes as grain aggregates. In the high-grade vein ores, coarse-grained Au–(Ag)–tellurides (calaverite, sylvanite, krennerite, and petzite) form a major part of quartz–telluride veins. Chalcopyrite forms separate monomineralic veins emplaced within the quartz–telluride veins. Spectacular textures among coarse-grained (up to 3 cm in diameter) tellurides, and micron-scale bamboo shoot-like grains are observed. Two- and three-phase telluride symplectites are common in the vein ores.Fluid inclusion studies suggest that the mineralizing fluids are a mixture of magmatic and meteoric fluids, that homogenized in the temperature range of 260–280 °C. Sulfur isotope compositions of pyrite and chalcopyrite (δ³⁴S − 1.64 to 1.91‰) support the origin of fluids from a deep source. It is suggested that faulting, temperature changes and variation in fS₂ and fTe₂ were major factors contributing to the two main types of mineralization and the differences between them. Early rapid cooling and subsequent slow cooling of the later fluids along fault and fracture zones were instrumental in formation of the two superposed ore types. Open-space filling and crack-sealing along fractures predominates over replacement during telluride mineralization. The Sandaowanzi deposit is a unique bonanza-grade accumulation of gold tellurides genetically related to subalkaline magmatism, which was genetically associated with Early Cretaceous regional extension.     

Native antimony in the Baogutu gold deposit (west Junggar,NW China): Its occurrence and origin

The Baogutu gold deposit, West Junggar (Xinjiang, NW China), is composed of quartz–sulfide veins and their stockworks and is hosted within an Early Carboniferous volcanic–sedimentary sequence. Three ore-forming paragenetic stages can be identified: coarse-grained quartz–sulfide vein (stage I), gold-bearing fine-grained quartz–sulfide vein (stage II), and native antimony-bearing calcite–sulfide veinlets (stage III). The estimated formation temperatures (approximately 360 to 220 °C), fS₂ (? 7 to ? 15 log units), and fO₂ (? 26 to ? 43 log units) decrease from stage I, through stage II, to stage III. The nature of the hydrothermal fluid changed from weakly acidic (pH: 5 to 6 at stage I) to alkaline (pH: > 7 at stage III).Two different occurrences of native antimony could be identified: one coexists with chalcopyrite and pyrrhotite, whereas the other occurs as isolate grains within calcite veins. Native antimony (up to 100 μm in size) contains minor amounts of As (2.0 to 2.7 wt.%); empirical formula Sb_0.95–0.96As_0.03–0.04. Decrease of temperature and fO₂ at high pH and low fS₂ conditions favored co-precipitation of native antimony–ullmannite assemblages and the decomposition of tetrahedrite. Native antimony crystallized later than the native gold, suggesting fractionation between Au and Sb during the hydrothermal evolution of the deposit.     

Mineralogy,chalcopyrite ReOs geochronology and sulfur isotope of the Hujiayu Cu deposit in the Zhongtiao Mountains,North China Craton: Implications for a Paleoproterozoic metamorphogenic copper mineralization

The Hujiayu Cu deposit, located in the Zhongtiao Mountains district of southern North China Craton, is hosted by graphite schist and dolomitic marble with disseminated to veinlet (stage I) and thick vein (stage II) mineralization. Stage I mineralization, characterized by stratabound, disseminated pyrite and chalcopyrite within the graphite schist host rock, formed at the syn-metamorphic stage. Graphite geothermometry showed that the host rock was subjected to an upper-greenschist to lower amphibolite metamorphism at a temperature range of 486 to 596 °C, averaging of 546 ± 35 °C (1 σ, n = 19). Stage II mineralization, consisting of brecciated dolomitic thick veins cemented by quartz-sulfide assemblages, was a product of metamorphic hydrothermal activity. This thick vein was subdivided into an early hydrothermal dolomitic alteration composing of dolomitic breccia with some cobaltiferous pyrite (stage IIa) and a late siliceous-copper mineralization consisting of quartz-sulfide assemblages (stage IIb). A clausthalite–siegenite–sphalerite–chalcopyrite mineral assemblage was observed in stage IIb, constraining the sulfur fugacity and selenium fugacity within − 18.7 to − 11.7 and − 21.7 to − 14.7, respectively. It was inferred stage IIb was marked by a drop in sulfur fugacity and a substantial increase in selenium fugacity after the major chalcopyrite precipitation. Calculations based on the compositions of cobaliterous pyrite and sphalerite reveal that the mineral assemblage at stage IIa formed at an approximately temperature range of 400 to 300 °C, whereas the minerals in stage IIb occurred at temperature of 256 ± 9 °C (1 σ, n = 7). Sulfides from stage I have δ³⁴S value ranging from 10.1 to 22.2‰ with an average value of 16.9 ± 3.4‰ (1 σ, n = 27), supporting the model that sulfides precipitated through thermochemical reduction of sulfate at sedimentary stage followed by metamorphic homogenization of δ³⁴S isotopic signatures. Sulfides from the stage II have δ³⁴S values in highly variable ranging from 3.4 to 19.2‰, indicating a rather complex source. Four chalcopyrite samples yielded a weighted model age of 1952 ± 39 Ma (1 σ, MSWD = 1.5), suggesting that the copper mineralization formed synchronously with regional metamorphism (1970–1850 Ma) and hence a Paleoproterozoic metamorphogenic copper mineralization is implicated. Therefore, we envisaged disseminated-veinlet mineralization formed during a metamorphic peak and the major hydrothermal copper mineralization occurred during the retrograde cooling.     

Origin of a barite-sulfide ore deposit in the Mykonos intrusion,cyclades: Trace element,isotopic, fluid inclusion and raman spectroscopy evidence

The polymetallic Mykonos vein system in the Cyclades, Greece, consists of 15 tension-gashes filled with barite, quartz, pyrite, sphalerite, chalcopyrite and galena in ca. 13.5 Ma, I-type, Mykonos monzogranite. Zones of silica and chlorite–muscovite alteration are associated with the veins and overprint pervasive silicification, phyllic and argillic alteration that affected large parts of the monzogranite. The mineralization cements breccias and consists of an early barite–silica–pyrite–sphalerite–chalcopyrite assemblage followed by later argentiferous galena. A combination of fluid inclusion and stable isotope data suggests that the barite and associated mineralization were deposited from fluids containing 2 to 17 wt.% NaCl equivalent, at temperatures of ~ 225° to 370 °C, under a hydrostatic pressure of ≤ 100 bars. The mineralizing fluids boiled and were saturated in H₂S and SO₂.Calculated δ¹⁸O_H2O and δD_H2O, initial ⁸⁷Sr/⁸⁶Sr isotope compositions and the trace and REEs elements contents are consistent with a model in which the mineralizing fluids were derived during alteration of the Mykonos intrusion and subsequently mixed with Miocene seawater. Heterogeneities in the calculated δ³⁴S_SO4^− 2 and δ³⁴S_H2S compositions of the ore fluids indicate two distinct sources for sulfur, namely of magmatic and seawater origin, and precipitation due to reduction of the SO₄^− 2 during fluid mixing. The physicochemical conditions of the fluids were pH = 5.0 to 6.2, logf_S2 = − 13.8 to − 12.5, logf_O2 = − 31.9 to − 30.9, logf_H2S(g) = − 1.9 to − 1.7, logf_Te2 = − 7.9 and logα(SO₄^− 2_(aq)/H₂S_(aq)) = + 2.6 to + 5.5. We propose that retrograde mesothermal hydrothermal alteration of the Mykonos monzogranite released barium and silica from the alkali feldspars. Barite was precipitated due to mixing of SO₄^− 2-rich Miocene seawater with the ascending Ba-rich magmatic fluid venting upwards in the pluton.     

S,O and Pb isotopic evidence on the origin of the İnkaya (Simav-Kütahya) Cu–Pb–Zn–(Ag) Prospect,NW Turkey

The İnkaya Cu–Pb–Zn–(Ag) prospect is a typical example of the hydrothermal mineralization occurring in the Menderes Massif, which crop out in Western Anatolia. The prospect located approximately 20 km west of Simav (Kütahya-Turkey) in northern part of the Menderes Massif have been characterized through the detailed examinations involving geological, mineralogical, whole-rock geochemistry, fluid inclusion, stable isotope and lead isotope.The İnkaya Cu–Pb–Zn–(Ag) prospect is located along an E–W-trending fault in the Cambrian Simav Metamorphics, which consist of quartz–muscovite schist, quartz–biotite schist, muscovite schist, biotite schist and the Arıkayası Formation, which is composed of marbles. Galena, sphalerite, chalcopyrite, pyrite and fahlore are the main minerals, and they are accompanied by small amounts of cerussite, anglesite, digenite, enargite, chalcocite, covellite, bornite, and Fe-oxides with gangue quartz. In addition to Pb, Zn, Cu, Ag, the ore samples contain substantial quantities of As, Cd and Bi and small amount of Au. Average contents of Cu, Pb, Zn and Ag are 77,400 ppm, 102,600 ppm, 6843 ppm and 203 ppm, respectively.The δ³⁴S values for galena, chalcopyrite and pyrite formed in the same stage vary in the range from − 1.7 to − 2.1‰ (average − 2.0), 0.1 to 0.3‰ (average 0.2) and − 1.5 to 2.6‰ (average + 1.5), respectively.δ³⁴S values for H₂S, representing the composition of the fluids responsible for the sulfide mineral formations and calculated from the δ³⁴S value are between − 2.77 and 1.33‰; it is consistent with the sulfur in sulfide minerals. δ¹⁸O_quartz values range from 11.3 to 16.4‰ and estimated δ¹⁸O_fluid values range from 5.4 to 10.6‰.Pyrite–galena and pyrite–chalcopyrite pairs calculated to determine equilibrium isotope temperatures based on δ³⁴S values are between 254.6 and 277.4 °C for pyrite–galena and 274.7 °C for pyrite–chalcopyrite. Sulfur and oxygen isotope values similar to the values for fluid equilibrated with an felsic magmatic source.Fluid inclusion studies on quartz of the same silicification stage coexisting with galena, sphalerite and chalcopyrite collected from the mineralized vein indicate that the temperature range of the fluids is 235 °C to 340 °C and that the salinities are 0.7 to 4.49 wt.% NaCl equivalent. The wide range of homogenization temperatures and relatively lower salinities of the fluid inclusions indicate that at least two different fluid generations were trapped in the quartz from only one fluid type. Also, lower salinities of fluid inclusion probably indicate mixing of meteoric water and magmatic fluid.The galena has ²⁰⁶Pb/²⁰⁴Pb values of 18.862–18.865, ²⁰⁷Pb/²⁰⁴Pb values of 15.707–15.711, and ²⁰⁸Pb/²⁰⁴Pb values of 39.033–39.042. The lead isotope values show a similarity with upper crustal values.     

Alteration and mineralization at the Zhibula Cu skarn deposit,Gangdese belt,Tibet

The Zhibula Cu skarn deposit contains 0.32 Mt. Cu metal with an average grade of 1.64% and is located in the Gangdese porphyry copper belt in southern Tibet. The deposit is a typical metasomatic skarn that is related to the interaction of magmatic–hydrothermal fluids and calcareous host rock. Stratiform skarn orebodies occur at the contact between tuff and marble in the Lower Jurassic Yeba Formation. Alteration zones generally grade from a fresh tuff to a garnet-bearing tuff, a garnet pyroxene skarn, and finally to a wollastonite marble. Minor endoskarn alteration zonations are also observed in the causative intrusion, which grade from a fresh granodiorite to a weakly chlorite-altered granodiorite, a green diopside-bearing granodiorite, and to a dark red-brown garnet-bearing granodiorite. Prograde minerals, which were identified by electron probe microanalysis include andradite–grossularite of various colors (e.g., red, green, and yellow) and green diopside. Retrograde metamorphic minerals overprint the prograde skarn, and are mainly composed of epidote, quartz, and chlorite. The ore minerals consist of chalcopyrite and bornite, followed by magnetite, molybdenite, pyrite, pyrrhotite, galena, and sphalerite. Three types of fluid inclusions are recognized in the Zhibula deposit, including liquid-rich two-phase inclusions (type L), vapor-rich two-phase inclusions (type V), and daughter mineral-bearing three-phase inclusions (type S). As the skarn formation evolved from prograde (stage I) to early retrograde (stage II) and later retrograde (stage III), the ore-forming fluids correspondingly evolved from high temperature (405–667 °C), high salinity (up to 44.0 wt.% NaCl equiv.), and high pressure (500–600 bar) to low-moderate temperature (194–420 °C), moderate-high salinity (10.1–18.3 and 30.0–44.2 wt.% NaCl equiv.), and low-moderate pressure (250–350 bar). Isotopic data of δ³⁴S (− 0.1‰ to − 6.8‰, estimated δ³⁴S_fluids = − 0.7‰), δD_H2O (− 91‰ to − 159‰), and δ¹⁸O_H2O (1.5‰ to 9.2‰) suggest that the ore-forming fluid and material came from magmatic–hydrothermal fluids that were associated with Miocene Zhibula intrusions. Fluid immiscibility likely occurred at the stage I and stage II during the formation of the skarn and mineralization. Fluid boiling occurred during the stage III, which is the most important Cu deposition mechanism for the Zhibula deposit.     

Geology,fluid inclusion and stable isotopes (O,S) of the Hetaoping distal skarn Zn-Pb deposit,northern Baoshan block,SW China

The Hetaoping zinc–lead deposit is located in the northern Baoshan block, Sanjiang region, SW China. The ore deposit comprises massive orebodies in the lower part and lenticular and vein-like orebodies in the upper part, both of which are hosted in the marbleized Upper Cambrian limestone and slate of the Hetaoping Formation. Three mineralization stages of Hetaoping skarn system have been recognized based on petrographic observation, which are pre-ore stage (pyroxene–garnet–actinolite–epidote–magnetite), syn-ore stage (sulfides–quartz–calcite–fluorite), and post-ore stage (calcite–quartz–chlorite). Andradite and hedenbergite are dominant in pre-ore garnet and pyroxene, respectively. Ore minerals consist of mainly pyrite, sphalerite, chalcopyrite, bornite and galena. Three types of fluid inclusions have been identified in Hetaoping, including primary two-phase (A type), primary three-phase (B type) and secondary two-phase (C type) inclusions. Based on fluid inclusion microthermometric study, the fluids forming the Hetaoping skarn minerals and sulfides evolved from high-moderate temperature (255–498 °C) and low-moderate salinity (5.0–18.0 wt.% NaCl equiv) in pre-ore stage, through moderate-low temperature (152–325 °C) and low salinity (0.4–14.2 wt.% NaCl equiv) in syn-ore stage, to low temperature (109–205 °C) and low salinity (0.9–10.0 wt.% NaCl equiv) in post-ore stage. The sulfide δ³⁴S values range from 3.7 to 7.1‰ (mean = 5.2‰, n = 29), indicative of a dominantly magmatic sulfur origin. Silicate and carbonate oxygen isotopes give calculated δ¹⁸O_H2O ranges of 3.9–11.1‰ in prograde stage, − 0.9 to 4.6‰ in early retrograde stage, and − 1.3 to 2.9‰ in late retrograde stage (syn-ore stage), The oxygen isotope data reveal that the prograde fluid in Hetaoping could be primarily magmatic, which has been mixed significantly with meteoric water in the late retrograde stage. Such a fluid mixing process is considered to be a key factor controlling ore precipitation.     

Cooperative extraction of metals from chalcopyrite by bio-oxidation and chemical oxidation

Chalcopyrite bio-dissolution plays an important role in the processing of copper sulfide ores. However, due to the slow dissolution rates of CuFeS₂, bio-dissolution processes have not yet found widespread application. In order to enhance the dissolution of chalcopyrite, a novel method for enhancing the dissolution using ozone was proposed and verified. The generated products in chalcopyrite dissolution process in the presence of Leptospirillum ferrooxidans and Acidithiobacillus thiooxidans was studied. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results indicate that a surface layer mainly consisting of jarosite and polysulfide (S_nⁿ⁻/S⁰) might be formed during biotic stage, which can be eliminated with the introduction of ozone. Electrochemical results show that ozone significantly increased the electrochemical reactivity of bioleached chalcopyrite, further proving that ozone enhanced the dissolution through destroying the surface layer. Hence, a bi-stage method for dissolution of chalcopyrite can be proposed.