Mineralium Deposita (v.45, #8)

Genesis of sediment-hosted stratiform copper–cobalt mineralization at Luiswishi and Kamoto, Katanga Copperbelt (Democratic Republic of Congo) by Hamdy A. El Desouky; Philippe Muchez; Adrian J. Boyce; Jens Schneider; Jacques L. H. Cailteux; Stijn Dewaele; Albrecht von Quadt (735-763).
The sediment-hosted stratiform Cu–Co mineralization of the Luiswishi and Kamoto deposits in the Katangan Copperbelt is hosted by the Neoproterozoic Mines Subgroup. Two main hypogene Cu–Co sulfide mineralization stages and associated gangue minerals (dolomite and quartz) are distinguished. The first is an early diagenetic, typical stratiform mineralization with fine-grained minerals, whereas the second is a multistage syn-orogenic stratiform to stratabound mineralization with coarse-grained minerals. For both stages, the main hypogene Cu–Co sulfide minerals are chalcopyrite, bornite, carrollite, and chalcocite. These minerals are in many places replaced by supergene sulfides (e.g., digenite and covellite), especially near the surface, and are completely oxidized in the weathered superficial zone and in surface outcrops, with malachite, heterogenite, chrysocolla, and azurite as the main oxidation products. The hypogene sulfides of the first Cu–Co stage display δ34S values (−10.3‰ to +3.1‰ Vienna Canyon Diablo Troilite (V-CDT)), which partly overlap with the δ34S signature of framboidal pyrites (−28.7‰ to 4.2‰ V-CDT) and have ∆34SSO4-Sulfides in the range of 14.4‰ to 27.8‰. This fractionation is consistent with bacterial sulfate reduction (BSR). The hypogene sulfides of the second Cu–Co stage display δ34S signatures that are either similar (−13.1‰ to +5.2‰ V-CDT) to the δ34S values of the sulfides of the first Cu–Co stage or comparable (+18.6‰ to +21.0‰ V-CDT) to the δ34S of Neoproterozoic seawater. This indicates that the sulfides of the second stage obtained their sulfur by both remobilization from early diagenetic sulfides and from thermochemical sulfate reduction (TSR). The carbon (−9.9‰ to −1.4‰ Vienna Pee Dee Belemnite (V-PDB)) and oxygen (−14.3‰ to −7.7‰ V-PDB) isotope signatures of dolomites associated with the first Cu–Co stage are in agreement with the interpretation that these dolomites are by-products of BSR. The carbon (−8.6‰ to +0.3‰ V-PDB) and oxygen (−24.0‰ to −10.3‰ V-PDB) isotope signatures of dolomites associated with the second Cu–Co stage are mostly similar to the δ13C (−7.1‰ to +1.3‰ V-PDB) and δ18O (−14.5‰ to −7.2‰ V-PDB) of the host rock and of the dolomites of the first Cu–Co stage. This indicates that the dolomites of the second Cu–Co stage precipitated from a high-temperature, host rock-buffered fluid, possibly under the influence of TSR. The dolomites associated with the first Cu–Co stage are characterized by significantly radiogenic Sr isotope signatures (0.70987 to 0.73576) that show a good correspondence with the Sr isotope signatures of the granitic basement rocks at an age of ca. 816 Ma. This indicates that the mineralizing fluid of the first Cu–Co stage has most likely leached radiogenic Sr and Cu–Co metals by interaction with the underlying basement rocks and/or with arenitic sedimentary rocks derived from such a basement. In contrast, the Sr isotope signatures (0.70883 to 0.71215) of the dolomites associated with the second stage show a good correspondence with the 87Sr/86Sr ratios (0.70723 to 0.70927) of poorly mineralized/barren host rocks at ca. 590 Ma. This indicates that the fluid of the second Cu–Co stage was likely a remobilizing fluid that significantly interacted with the country rocks and possibly did not mobilize additional metals from the basement rocks.
Keywords: Central African Copperbelt; D.R. Congo; Stratiform Cu–Co mineralization; Stable (S, C, O) and radiogenic (Rb–Sr) isotopes; Bacterial and thermochemical sulfate reduction

Concentrations of platinum group elements (PGE), Ag, As, Au, Bi, Cd, Co, Mo, Pb, Re, Sb, Se, Sn, Te, and Zn, have been determined in base metal sulfide (BMS) minerals from the western branch (402 Trough orebodies) of the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada. The sulfide assemblage is dominated by pyrrhotite, with minor pentlandite, chalcopyrite, and pyrite, and they represent monosulfide solid solution (MSS) cumulates. The aim of this study was to establish the distribution of the PGE among the BMS and platinum group minerals (PGM) in order to understand better the petrogenesis of the deposit. Mass balance calculations show that the BMS host all of the Co and Se, a significant proportion (40–90%) of Os, Pd, Ru, Cd, Sn, and Zn, but very little (<35%) of the Ag, Au, Bi, Ir, Mo, Pb, Pt, Rh, Re, Sb, and Te. Osmium and Ru are concentrated in equal proportions in pyrrhotite, pentlandite, and pyrite. Cobalt and Pd (∼1 ppm) are concentrated in pentlandite. Silver, Cd, Sn, Zn, and in rare cases Au and Te, are concentrated in chalcopyrite. Selenium is present in equal proportions in all three BMS. Iridium, Rh, and Pt are present in euhedrally zoned PGE sulfarsenides, which comprise irarsite (IrAsS), hollingworthite (RhAsS), PGE-Ni-rich cobaltite (CoAsS), and subordinate sperrylite (PtAs2), all of which are hosted predominantly in pyrrhotite and pentlandite. Silver, Au, Bi, Mo, Pb, Re, Sb, and Te are found predominantly in discrete accessory minerals such as electrum (Au–Ag alloy), hessite (Ag2Te), michenerite (PdBiTe), and rhenium sulfides. The enrichment of Os, Ru, Ni, and Co in pyrrhotite, pentlandite, and pyrite and Ag, Au, Cd, Sn, Te, and Zn in chalcopyrite can be explained by fractional crystallization of MSS from a sulfide liquid followed by exsolution of the sulfides. The early crystallization of the PGE sulfarsenides from the sulfide melt depleted the MSS in Ir and Rh. The bulk of Pd in pentlandite cannot be explained by sulfide fractionation alone because Pd should have partitioned into the residual Cu-rich liquid and be in chalcopyrite or in PGM around chalcopyrite. The variation of Pd among different pentlandite textures provides evidence that Pd diffuses into pentlandite during its exsolution from MSS. The source of Pd was from the small quantity of Pd that partitioned originally into the MSS and a larger quantity of Pd in the nearby Cu-rich portion (intermediate solid solution and/or Pd-bearing PGM). The source of Pd became depleted during the diffusion process, thus later-forming pentlandite (rims of coarse-granular, veinlets, and exsolution flames) contains less Pd than early-forming pentlandite (cores of coarse-granular).
Keywords: Platinum group elements; Sulfides; Sulfarsenides; Sudbury; Canada; Laser ablation ICP-MS; Palladium enrichment in pentlandite

Bulk δ 34Srock values, sulfur contents, and magnetic susceptibility were determined for 12 gold-related granitoid intrusions in southwestern New Brunswick, the Canadian Appalachians. The sulfur isotope compositions of sulfide minerals in some of the granitoid samples were also analyzed. This new dataset was used to characterize two distinctive groups of granitoids: (1) a Late Devonian granitic series (GS) and (2) a Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS). The GS rocks have a large range in δ 34S values of −7.1‰ to +13‰ with an average of 2.2 ± 5.0‰ (1σ), low bulk-S contents (33 to 7,710 ppm) and low magnetic susceptibility values (<10−4 SI), consistent with reduced ilmenite-series granites. The GMS rocks have a relatively narrower variation in δ 34S values of −4.4‰ to +7.3‰ with an average 1.2 ± 2.9‰ but with larger ranges in bulk-S contents (45 to 11,100 ppm) and high magnetic susceptibility values (>10−3 SI), indicative of oxidized magnetite-series granites. The exceptions for the GMS rocks are the Lake George granodiorite and Tower Hill granite that display reduced characteristics, which may have resulted from interaction of the magmas forming these intrusions with graphite- or organic carbon-bearing sedimentary rocks. The bulk δ 34S values and S contents of the GMS rocks are interpreted in terms of selective assimilation–fractional crystallization (SAFC) processes. Degassing processes may account for the δ 34S values and S contents of some GS rocks. The characteristics of our sulfur isotope and abundance data suggest that mineralizing components S and Au in intrusion-related gold systems are dominantly derived from magmatic sources, although minor contaminants derived from country rocks are evident. In addition, the molar sulfate to sulfide ratio in a granitic rock sample can be calculated from the δ 34Srock value of the whole-rock sample and the δ 34Ssulfide (or δ 34Ssulfate) value of sulfide and/or sulfate mineral in the sample on the basis of S-isotope fractionation and mass balance under the condition of magmatic equilibrium. This may be used to predict the speciation of sulfur in granitic rocks, which can be a potential exploration tool for intrusion-related gold systems.
Keywords: Sulfur isotopic composition; Sulfate/sulfide ratios; Redox condition; Granitoids; Intrusion-related gold systems; Appalachians; Canada

Formation of the Vysoká–Zlatno Cu–Au skarn–porphyry deposit, Slovakia by Peter Koděra; Jaroslav Lexa; Anthony E. Fallick (817-843).
The central zone of the Miocene Štiavnica stratovolcano hosts several occurrences of Cu–Au skarn–porphyry mineralisation, related to granodiorite/quartz–diorite porphyry dyke clusters and stocks. Vysoká–Zlatno is the largest deposit (13.4 Mt at 0.52% Cu), with mineralised Mg–Ca exo- and endoskarns, developed at the prevolcanic basement level. The alteration pattern includes an internal K- and Na–Ca silicate zone, surrounded by phyllic and argillic zones, laterally grading into a propylitic zone. Fluid inclusions in quartz veinlets in the internal zone contain mostly saline brines with 31–70 wt.% NaCl eq. and temperatures of liquid–vapour homogenization (Th) of 186–575°C, indicating fluid heterogenisation. Garnet contains inclusions of variable salinity with 1–31 wt.% NaCl eq. and Th of 320–360°C. Quartz–chalcopyrite veinlets host mostly low-salinity fluid inclusions with 0–3 wt.% NaCl eq. and Th of 323–364°C. Data from sphalerite from the margin of the system indicate mixing with dilute and cooler fluids. The isotopic composition of fluids in equilibrium with K-alteration and most skarn minerals (both prograde and retrograde) indicates predominantly a magmatic origin (δ18Ofluid 2.5–12.3‰) with a minor meteoric component. Corresponding low δDfluid values are probably related to isotopic fractionation during exsolution of the fluid from crystallising magma in an open system. The data suggest the general pattern of a distant source of magmatic fluids that ascended above a zone of hydraulic fracturing below the temperature of ductile–brittle transition. The magma chamber at ∼5–6 km depth exsolved single-phase fluids, whose properties were controlled by changing PT conditions along their fluid paths. During early stages, ascending fluids display liquid–vapour immiscibility, followed by physical separation of both phases. Low-salinity liquid associated with ore veinlets probably represents a single-phase magmatic fluid/magmatic vapour which contracted into liquid upon its ascent.
Keywords: Štiavnica stratovolcano; Skarn; Porphyry; Stable isotopes; Fluid inclusions; Copper–gold; Slovakia