Brine pool deposition for the Zn–Pb–Cu massive sulphide deposits of the Bathurst mining camp, New Brunswick, Canada. I. Comparisons with the Iberian pyrite belt

The Ordovician Zn–Pb–Cu massive sulphide ore deposits of the Bathurst mining camp share many features with those of the Devonian/Carboniferous Iberian pyrite belt, particularly the tendency to large size (tonnage and metal content); shape, as far as can be determined after allowing for deformation; metal content, particularly Fe/Cu, Pb/Zn and Sn; mineral assemblages (pyrite + arsenopyrite ± pyrrhotite and lack or rarity of sulphates); sulphide textures (particularly framboidal pyrite); lack of chimney structures and rubble mounds; irregular metal or mineral zoning; and the low degree of zone refining compared to Hokuroku ores. The major differences between the provinces are the lack of vent complexes and the presence of Sn–Cu ores in the Iberian pyrite belt. There are also similarities in the geological setting of the two camps: both lie within continental terranes undergoing arc-continent and continent–continent collision, and in each case massive sulphide mineralisation followed ophiolite obduction; the ore deposits are associated with bimodal volcanic rocks derived from MORB and continental crust and marine shales; and mineralisation was locally accompanied or followed by deposition of iron formations.Fluid inclusion data from veins in stockworks from at least six of the Iberian massive sulphide deposits point to sulphide deposition having taken place in basins containing mostly spent saline, ore-forming fluids (brine pools), and it is suggested that most of the major features of the Bathurst deposits can be explained by similar processes. The proposed model is largely independent of ocean sulphate and O₂ content, whereas low values of each are requisites for the current, spreading-plume model of sulphide deposition in the Bathurst camp.     

Geological features and origin of the Huize carbonate-hosted Zn–Pb–(Ag) District, Yunnan, South China

The Huize Zn–Pb–(Ag) district, in the Sichuan–Yunnan–Guizhou Zn–Pb–(Ag) metallogenic region, contains significant high-grade, Zn–Pb–(Ag) deposits. The total metal reserve of Zn and Pb exceeds 5 Mt. The district has the following geological characteristics: (1) high ore grade (Zn + Pb ≥ 25 wt.%); (2) enrichment in Ag and a range of other trace elements (Ge, In, Ga, Cd, and Tl), with galena, sphalerite, and pyrite being the major carriers of Ag, Ge, Cd and Tl; (3) ore distribution controlled by both structural and lithological features; (4) simple and limited wall-rock alteration; (5) mineral zonation within the orebodies; and (6) the presence of evaporite layers in the ore-hosting wall rocks of the Early Carboniferous Baizuo Formation and the underlying basement.Fluid-inclusion and isotope geochemical data indicate that the ore fluid has homogenisation temperatures of 165–220 °C, and salinities of 6.6–12 wt.% NaCl equiv., and that the ore-forming fluids and metals were predominantly derived from the Kunyang Group basement rocks and the evaporite-bearing rocks of the cover strata. Ores were deposited along favourable, specific ore-controlling structures. The new laboratory and field studies indicate that the Huize Zn–Pb–(Ag) district is not a carbonate-replacement deposit containing massive sulphides, but rather the deposits can be designated as deformed, carbonate-hosted, MVT-type deposits. Detailed study of the deposits has provided new clues to the localisation of concealed orebodies in the Huize Zn–Pb–(Ag) district and of the potential for similar carbonate-hosted sulphide deposits elsewhere in NE Yunnan Province, as well as the Sichuan–Yunnan–Guizhou Zn–Pb–(Ag) metallogenic region.     

Geochronological framework and Pb, Sr isotope geochemistry of the Qingchengzi Pb–Zn–Ag–Au orefield, Northeastern China

The Qingchengzi orefield in northeastern China, is a concentration of several Pb–Zn, Ag, and Au ore deposits. A combination of geochronological and Pb, Sr isotopic investigations was conducted. Zircon SHRIMP U–Pb ages of 225.3 ± 1.8 Ma and 184.5 ± 1.6 Ma were obtained for the Xinling and Yaojiagou granites, respectively. By step-dissolution Rb–Sr dating, ages of 221 ± 12 Ma and 138.7 ± 4.1 Ma were obtained for the sphalerite of the Zhenzigou Zn–Pb deposit and pyrargyrite of the Ag ore in the Gaojiabaozi Ag deposit, respectively. Pb isotopic ratios of the Ag ore at Gaojiabaozi (²⁰⁶Pb/²⁰⁴Pb = 18.38 to 18.53) are higher than those of the Pb–Zn ores (²⁰⁶Pb/²⁰⁴Pb = 17.66 to 17.96; Chen et al. [Chen, J.F., Yu, G., Xue, C.J., Qian, H., He, J.F., Xing, Z., Zhang, X., 2005. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone, northeastern China. Science in China Series D 48, 467–476.]). Triassic granites show low Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb = 17.12 to 17.41, ²⁰⁷Pb/²⁰⁴Pb = 15.47 to 15.54, ²⁰⁸Pb/²⁰⁴Pb = 37.51 to 37.89) and metamorphic rocks of the Liaohe Group have high ratios (²⁰⁶Pb/²⁰⁴Pb = 18.20 to 24.28 and 18.32 to 20.06, ²⁰⁷Pb/²⁰⁴Pb = 15.69 to 16.44 and 15.66 to 15.98, ²⁰⁸Pb/²⁰⁴Pb = 37.29 to 38.61 and 38.69 to 40.00 for the marble of the Dashiqiao Formation and schist of the Gaixian Formation, respectively).Magmatic activities at Qingchengzi and in adjacent regions took place in three stages, and each contained several magmatic pulses: ca. 220 to 225 Ma and 211 to 216 Ma in the Triassic; 179 to 185 Ma, 163 to 168 Ma, 155 Ma and 149 Ma in the Jurassic, as well as ca. 140 to 130 Ma in the Early Cretaceous. The Triassic magmatism was part of the Triassic magmatic belt along the northern margin of the North China Craton produced in a post-collisional extensional setting, and granites in it formed by crustal melting induced by mantle magma. The Jurassic and Early Cretaceous magmatism was related to the lithospheric delamination in eastern China. The Triassic is the most important metallogenic stage at Qingchengzi. The Pb–Zn deposits, the Pb–Zn–Ag ore at Gaojiabaozi, and the gold deposits were all formed in this stage. They are temporally and spatially associated with the Triassic magmatic activity. Mineralization is very weak in the Jurassic. Ag ore at Gaojiabaozi was formed in the Early Cretaceous, which is suggested by the young Rb–Sr isochron age, field relations, and significantly different Pb isotopic ratios between the Pb–Zn–Ag and Ag ores. Pb isotopic compositions of the Pb–Zn ores suggest binary mixing for the source of the deposits. The magmatic end-member is the Triassic granites and the other metamorphic rocks of the Liaohe Group. Slightly different proportions of the two end-members, or an involvement of materials from hidden Cretaceous granites with slightly different Pb isotopic ratios, is postulated to interpret the difference of Pb isotopic compositions between the Pb–Zn–(Ag) and Ag ores. Sr isotopic ratios support this conclusion. At the western part of the Qingchengzi orefield, hydrothermal fluid driven by the heat provided by the now exposed Triassic granites deposited ore-forming materials in the low and middle horizons of the marbles of the Dashiqiao Formation near the intrusions to form mesothermal Zn–Pb deposits. In the eastern part, hydrothermal fluids associated with deep, hidden Triassic intrusions moved upward along a regional fault over a long distance and then deposited the ore-forming materials to form epithermal Au and Pb–Zn–Ag ores. Young magmatic activities are all represented by dykes across the entire orefield, suggesting that the corresponding main intrusion bodies are situated in the deep part of the crust. Among these, only intrusions with age of ca. 140 Ma might have released sufficient amounts of fluid to be responsible for the formation of the Ag ore at Gaojiabaozi.Our age results support previous conclusions that sphalerite can provide a reliable Rb–Sr age as long as the fluid inclusion phase is effectively separated from the “sulfide” phase. Our work suggests that the separation can be achieved by a step-resolution technique. Moreover, we suggest that pyrargyrite is a promising mineral for Rb–Sr isochron dating.     

Stratigraphy and base metal mineralization in the Otavi Mountain Land, Northern Namibia—a review and regional interpretation

Sediment-hosted base metal sulfide deposits in the Otavi Mountain Land occur in most stratigraphic units of the Neoproterozoic Damara Supergroup, including the basal Nosib Group, the middle Otavi Group and the uppermost Mulden Group. Deposits like Tsumeb (Pb–Cu–Zn–Ge), Kombat (Cu–Pb–Zn), Berg Aukas (Zn–Pb–V), Abenab West (Pb–Zn–V) all occur in Otavi Group dolostones, whereas siliciclastic and metavolcanic rocks host Cu–(Ag) or Cu–(Au) mineralization, respectively. The Tsumeb deposit appears to have been concentrated after the peak of the Damara orogeny at around 530 Ma as indicated by radiometric age data.Volcanic hosted Cu–(Au) deposits (Neuwerk and Askevold) in the Askevold Formation may be related to ore forming processes during continental rifting around 746 Ma. The timing of carbonate-hosted Pb–Zn deposits in the Abenab Subgroup at Berg Aukas and Abenab is not well constrained, but the stable (S, O, C) and Pb isotope as well as the ore fluid characteristics are similar to the Tsumeb-type ores. Regional scale ore fluid migration typical of MVT deposits is indicated by the presence of Pb–Zn occurrences over 2500 km² within stratabound breccias of the Elandshoek Formation. Mulden Group siliciclastic rocks host the relatively young stratiform Cu–(Ag) Tschudi resource, which is comparable to Copperbelt-type sulfide ores.     

Geology and wall rock alteration at the Hercynian Draa Sfar Zn–Pb–Cu massive sulphide deposit, Morocco

Draa Sfar is a siliciclastic–felsic, volcanogenic massive sulphide (VMS) Zn–Pb–Cu deposit located 15 km north of Marrakesh within the Jebilet massif of the western Moroccan Meseta. The Draa Sfar deposit occurs within the Sarhlef series, a volcano-sedimentary succession that hosts other massive sulphide deposits (e.g., Hajar, Kettara) within the dominantly siliciclastic sedimentary succession of the lower Central Jebilet. At Draa Sfar, the footwall lithofacies are dominated by grey to black argillite, carbonaceous argillite and intercalated siltstone with localized rhyodacitic flows and domes, associated in situ and transported autoclastic deposits, and lesser dykes of aphanitic basalt and gabbro. Thin- to thick-bedded, black carbonaceous argillite, minor intercalated siltstone, and a large gabbro sill dominate the hanging wall lithofacies. The main lithologies strike NNE–SSW, parallel to a pronounced S1 foliation, and have a low-grade, chlorite–muscovite–quartz–albite–oligoclase metamorphic assemblage. The Draa Sfar deposit consists of two stratabound sulphide orebodies, Tazakourt to the south and Sidi M'Barek to the north. Both orebodies are hosted by argillite in the upper part of the lower volcano-sedimentary unit. The Tazakourt and Sidi M'Barek orebodies are highly deformed, sheet-like bodies of massive pyrrhotite (up to 95% pyrrhotite) with lesser sphalerite, galena, chalcopyrite, and pyrite. The Draa Sfar deposit formed within a restricted, sediment-starved, fault-controlled, anoxic, volcano-sedimentary rift basin. The deposit formed at and below the seafloor within anoxic, pelagic muds.The argillaceous sedimentary rocks that surround the Draa Sfar orebodies are characterized by a pronounced zonation of alteration assemblages and geochemical patterns. In the more proximal volcanic area to the south, the abundance of medium to dark green chlorite progressively increases within the argillite toward the base of the Tazakourt orebody. Chlorite alteration is manifested by the replacement of feldspar and a decrease in muscovite abundance related to a net addition of Fe and Mg and a loss of K and Na. In the volcanically distal and northern Sidi M'Barek orebody alteration within the footwall argillite is characterized by a modal increase of sericite relative to chlorite. A calcite–quartz–muscovite assemblage and a pronounced decrease in chlorite characterize argillite within the immediate hanging wall to the entire Draa Sfar deposit. The sympathetic lateral change from predominantly sericite to chlorite alteration within the footwall argillite with increasing volcanic proximity suggests that the higher temperature part of the hydrothermal system is coincident with a volcanic vent defined by localized rhyodacitic flow/domes within the footwall succession.     

The geochemistry, mineralogy and maturity of gossans derived from volcanogenic Zn–Pb–Cu deposits of the eastern Lachlan Fold Belt, NSW, Australia

The Eastern Highlands of Australia have probably been in existence since the Late Cretaceous or earlier and so there has been ample time for mature gossan profiles to form over outcropping volcanogenic Zn–Pb–Cu mineralisation in the eastern Lachlan Fold Belt. The mature gossan profiles are characterised by the upward progression from supergene sulfides to secondary sulfates, carbonates and phosphates into a Fe-oxide dominated surficial capping which may contain boxwork textures after the original sulfides (as at the Woodlawn massive sulfide deposit). However, the region has locally been subjected to severe erosion and the weathering profile over many deposits is incomplete (immature) with carbonate and phosphate minerals, especially malachite, being found in surficial material. These immature gossans contain more Cu, Pb and Zn but lower As, Sn (and probably Au) than the mature gossans. Although Pb is probably the best single pathfinder for Zn–Pb–Cu VHMS deposits of the eastern Lachlan Fold Belt, Ag, As, Au, Bi, Mo, Sb and Sn are also useful, with most of these elements able to be concentrated in substantial amounts in Fe oxides and alunite–jarosite minerals.     

Outokumpu revisited: New mineral deposit model for the mantle peridotite-associated Cu–Co–Zn–Ni–Ag–Au sulphide deposits

The metaturbidites of the Palaeoproterozoic Jormua–Outokumpu thrust belt in eastern Finland enclose m- to km-scale ultramafic massifs that are distributed over an area of more than 5000 km². These bodies, which almost entirely consist of highly depleted mantle peridotites (now metaserpentinites and metaperidotites), are intimately associated with massive to semimassive, polymetallic Cu–Co–Zn–Ni–Ag–Au sulphide deposits that sustained mining in the region between 1913 and 1988. Currently, one deposit (Kylylahti) is proceeding into a definitive feasibility study emphasising the renewed economic interest for Outokumpu-type deposits.The origin of these Outokumpu-type Cu–Co–Zn–Ni–Ag–Au deposits is now re-interpreted to be polygenetic. First, their formation requires deposition of a Cu-rich proto-ore within peridotitic sea floor at  1950 Ma. Close modern analogues to the proto-ore setting include, for example, the Logatchev and Rainbow fields at the Mid-Atlantic Ridge, where venting of high-T–low-pH hydrothermal fluid resulted in accumulations of Cu–Zn–Co–Ag–Au sulphides on serpentinised ultramafic seafloor. Second, the Ni-rich composition of Outokumpu sulphide ores calls for a separate source for nickel: Some 40 Ma after the deposition of the Cu-rich proto-ore – concomitant with the obduction of the ultramafic massifs – disseminated Ni sulphides formed through chemical interaction between obducting peridotite massifs and adjacent black schists. This process was related to listwaenite–birbirite type carbonate–silica alteration at margins of the ultramafic massifs. Due to this alteration, silicate nickel was released from the primary Fe–Mg silicates and redeposited as Ni sulphides in the alteration fringes of the massifs.We propose that syntectonic mixing of these two “end-member” sulphides, i.e., the primary Cu-rich proto-ore and the secondary Ni-sulphide disseminations, resulted in the uncommon metal combination of the Outokumpu-type sulphides. Late tectonic solid-state re-mobilisation, related to the duplexing of the ore by isoclinal folding, upgraded the sulphides into economic deposits.     

Reconstruction of the hydrothermal history of the Cu–Ag vein-type mineralisation at Dikulushi, Kundelungu foreland, Katanga, D.R. Congo

The Kundelungu foreland, north of the Lufilian arc in the Democratic Republic of Congo, contains a number of various vein-type and stratiform copper mineralisations. The geodynamic context and metallogenesis of these mineral occurrences remain enigmatic. Currently, the vein-type Cu–Ag ore deposit at Dikulushi is the most significant deposit in the region. Mineralisation at Dikulushi comprises two major styles: 1) a polysulphide assemblage (Zn–Pb–Fe–Cu–As) within brecciated rocks along an anticlinal closure; and 2) a vein-hosted Cu–Ag assemblage. Petrographic and fluid inclusion studies indicate that the early Zn–Pb–Fe–Cu–As assemblage formed from a high-salinity Ca–Na–Cl fluid of modest temperature (135–172 °C). The later, economically more significant vein-related Cu–Ag mineralisation formed from intermediate salinity, lower temperature (46–82 °C) Na–Cl fluids. Weathering of the sulphide minerals resulted in a supergene enrichment with the formation of secondary Cu-minerals.     

Lewis Ponds, a hybrid carbonate and volcanic-hosted polymetallic massive sulphide deposit, New South Wales, Australia

The Lewis Ponds Zn–Pb–Cu–Ag–Au deposit, located in the eastern Lachlan Fold Belt, central western New South Wales, exhibits the characteristics of both volcanic-hosted massive sulphide and carbonate-hosted replacement deposits. Two stratabound massive to disseminated sulphide zones, Main and Toms, occur in a tightly folded Upper Silurian sequence of marine felsic volcanic and sedimentary rocks. They have a combined indicated resource of 5.7 Mt grading 3.5% Zn, 2.0% Pb, 0.19% Cu, 97 g/t Ag and 1.9 g/t Au. Main Zone is hosted by a thick unit of poorly sorted mixed provenance breccia, limestone-clast breccia and quartz crystal-rich sandstone, whereas Toms Zone occurs in the overlying siltstone. Pretectonic carbonate–chalcopyrite–pyrite and quartz–pyrite stringer veins occur in the footwall porphyritic dacite, south of Toms Zone. Strongly sheared dolomite–chalcopyrite–pyrrhotite veins directly underlie the Toms massive sulphide lens. The mineralized zones consist predominantly of pyrite, sphalerite and galena. Paragenetically early framboidal, dendritic and botryoidal pyrite aggregates and tabular pyrrhotite pseudomorphs of sulphate occur throughout the breccia and sandstone beds that host Main Zone, but are rarely preserved in the annealed massive sulphide in Toms Zone. Main and Toms zones are associated with a semi-conformable hydrothermal alteration envelope, characterized by texturally destructive chlorite-, dolomite- and quartz-rich assemblages. Dolomite, chlorite, quartz, calcite and sulphides have selectively replaced breccia and sandstone beds in the Main Zone host sequence, whereas the underlying porphyritic dacite is weakly sericite altered. Vuggy and botryoidal textures resulted from partial dissolution of the dolomite-altered sedimentary rocks and unimpeded growth of base metal sulphides, carbonate and quartz into open cavities. The intense chlorite-rich alteration assemblage, underlying Toms Zone, grades outward into a weak pervasive sericite–quartz assemblage with distance from the massive sulphide lens. Limestone clasts and hydrothermal dolomite at Lewis Ponds are enriched in light carbon and oxygen isotopes. The dolomite yielded ¹³C_VPDB values of –11 to +1 and ¹⁸O_VSMOW values of 6 to 16. Liquid–vapour fluid inclusions in the dolomite have low salinities (1.4–7.7 equiv. wt% NaCl) and homogenization temperatures (166–232°C for 1,000 m water depth). Dolomitization probably involved fluid mixing or fluid–rock interactions between evolved heated seawater and the limestone-bearing facies, prior to and during mineralization. ³⁴S_VCDT values range from 2.0 to 5.0 in the massive sulphide and 3.9 to 7.4 in the footwall carbonate–chalcopyrite–pyrite stringer veins, indicating that the hydrothermal fluid may have contained mamgatic sulphur and a component of partially reduced seawater. The sulphide mineral assemblages at Lewis Ponds are consistent with moderate to strongly reduced conditions during diagenesis and mineralization. Low temperature dolomitization of limestone-bearing facies in the Main Zone host sequence created secondary porosity and provided a reactive host for fluid-rock interactions. Main Zone formed by lateral fluid flow and sub-seafloor replacement of the poorly sorted breccia and sandstone beds. Base metal sulphide deposition probably resulted from dissolution of dolomite, fluid mixing and increased fluid pH. Pyrite, sphalerite and galena precipitated from a relatively low temperature, 150–250°C hydrothermal fluid. In contrast, Toms Zone was emplaced into fine-grained sediment at or near the seafloor, above a zone of focused up-flowing hydrothermal fluids. Copper-rich assemblages were deposited in the Toms Zone footwall and massive sulphide lenses in Main and Toms zones as the hydrothermal system intensified. During the D₁ deformation, fracture-controlled fluids within the Lewis Ponds fault zone and adjacent footwall volcanic succession remobilized sulphides into syntectonic quartz veins. Lewis Ponds is a rare example of a synvolcanic sub-seafloor hydrothermal system developed within fossiliferous limestone-bearing facies. The close spatial association between limestone, hydrothermal dolomite, massive sulphide and dacite provides a basis for new exploration targets elsewhere in New South Wales.Editorial handling: D. Lentz     

Laser microprobe sulphur isotope analysis of arsenopyrite: experimental calibration and application to the Boliden Au–Cu–As massive sulphide deposit

Metamorphic remobilization of arsenopyrite-rich ores is a globally important process which can lead to significant concentrations of gold. In order to understand this and related processes, relations of sulphur isotopes can give a number of important clues. To resolve such relations in detail, we have successfully calibrated and applied a laser combustion system for in situ analysis of sulphur isotopic compositions of arsenopyrite. Experimental calibration of the laser fractionation factor (+0.4‰) was obtained by using compositionally and isotopically homogeneous natural samples from ore deposits at Boliden (Sweden) and Freiberg (Germany); subsequent to detailed microscopic study, the S isotope ratios of these samples were measured by conventional and laser combustion techniques.The present application to different types of arsenopyrite in the Palaeoproterozoic metamorphosed VHMS ores of the Boliden Au–Cu–As deposit, Skellefte district, northern Sweden, shows that the sulphur isotope composition of arsenopyrite is essentially unmodified during medium-grade metamorphic recrystallization and remobilization. Here, massive arsenopyrite ore is crosscut by later veins that carry a complex quartz–sulphosalt–sulphide assemblage. The latter ore type is markedly Au-rich compared to the host ore, and thus of significant economic interest. We find that both ore types exhibit very similar sulphur isotope compositions, ca. +2‰ to +3‰ (V-CDT), which is similar to most massive sulphide deposits in the Skellefte district. Thus, the crosscutting Au-rich vein ore has inherited the sulphur isotope composition from sulphur liberated by metamorphic reactions affecting the massive ore, and most likely also inherited the Au through this mechanism. The latter finding clearly has important implications both for the general discussion on, and the prospecting for, similar high-grade Au ores in this world-class mining region.     

Modeling of fluid pressure evolution related to sediment loading and thrust faulting in the Lanping basin: Implications for the formation of the Jinding Zn–Pb deposit, Yunnan, China

The Jinding Zn–Pb deposit occurs in Cretaceous and Paleocene siliciclastic rocks (mainly sandstones) in the Meso-Cenozoic Lanping basin, western Yunnan, China. With a reserve of approximately 200 Mt of ore containing 6.1% Zn and 1.3% Pb, Jinding is the largest sandstone-hosted Zn–Pb deposit in the world. Most previous studies assumed that the mineralizing fluids were derived from within the basin (including meteoric recharge), and the fluid flow was driven by topographic relief under a hydrostatic regime. In contrast, we propose that the mineralizing system was strongly overpressured based on observations of hydraulic fractures and fluid inclusion data. Numerical modeling results indicate that the overpressures could not have been produced by normal sediment compaction. Thrust faulting and input of mantle-derived fluids are likely responsible for the building-up of the high overpressures. The special hydrodynamic regime and potential contribution of mantle-derived fluids to the mineralizing system distinguish Jinding from other known sedimentary basin-related Pb–Zn deposits.     

As–(Ag) sulphide veins in the Spanish Central System: further evidence for a hydrothermal event of Permian age

The Spanish Central System (SCS) has been subjected to repeated deformation and fluid flow events which have produced both sulphide-bearing and barren vein systems. Although several hydrothermal episodes took place between 300 and 100 Ma, fluid circulation during the Permian was especially important, giving rise to a range of different types of deposits. This study presents a multidisciplinary approach leading to the characterisation of the chemistry and age of the hydrothermal fluids that produced the As–(Ag) mineralised stockwork of Mónica mine (Bustaviejo, Madrid). Fluid inclusion data indicate the presence of two different fluids. An initial ore stage (I) formed from a low- to moderate salinity (3–8 wt.% eq. NaCl) H₂O–NaCl–CO₂–CH₄ fluid, at minimum trapping temperature of 350±15 °C and 0.3 kbar. A second H₂O–NaCl fluid is found in three types of fluid inclusions: a high temperature and low salinity type (340±20 °C; 0.8–3.1 wt.% eq. NaCl) also associated to ore stage I, a moderate temperature and very low salinity type (160–255 °C; 0–1.5 wt.% eq. NaCl) represented in ore stage III, and a very low temperature and hypersaline type (60–70 °C; 30–35 wt.% NaCl), unrelated to the mineralising stages and clearly postdating the previous types. ⁴⁰Ar–³⁹Ar dating on muscovite from the early As–Fe stage (I) has provided an age of 286±4 Ma, synchronous with the late emplacement phases of La Cabrera plutonic massif (288±5 Ma) and with other Permian hydrothermal events like Sn–W skarns and W–(Sn) sulphide veins. δ¹⁸O of water in equilibrium with stage I quartz (5.3–7.7‰), δD of water in equilibrium with coexisting muscovite (−16.0‰ to −2.0‰), and sulphide δ³⁴S (1.5–3.6‰) values are compatible with waters that leached metamorphic rocks. The dominant mechanism of the As–(Ag) deposition was mixing and dilution processes between aqueous–carbonic and aqueous fluids for stage I (As–Fe), and nearly isobaric cooling processes for stages II (Zn–Cu–Sn) and III (Pb–Ag). The origin and hydrothermal evolution of As–(Ag) veins is comparable to other hydrothermal Permian events in the Spanish Central System.     

2: Hydrothermal ore deposits related to post-orogenic extensional magmatism and core complex formation: The Rhodope Massif of Bulgaria and Greece

The Rhodope Massif in southern Bulgaria and northern Greece hosts a range of Pb–Zn–Ag, Cu–Mo and Au–Ag deposits in high-grade metamorphic, continental sedimentary and igneous rocks. Following a protracted thrusting history as part of the Alpine–Himalayan collision, major late orogenic extension led to the formation of metamorphic core complexes, block faulting, sedimentary basin formation, acid to basic magmatism and hydrothermal activity within a relatively short period of time during the Early Tertiary. Large vein and carbonate replacement Pb–Zn deposits hosted by high-grade metamorphic rocks in the Central Rhodopean Dome (e.g., the Madan ore field) are spatially associated with low-angle detachment faults as well as local silicic dyke swarms and/or ignimbrites. Ore formation is essentially synchronous with post-extensional dome uplift and magmatism, which has a dominant crustal magma component according to Pb and Sr isotope data. Intermediate- and high-sulphidation Pb–Zn–Ag–Au deposits and minor porphyry Cu–Mo mineralization in the Eastern Rhodopes are predominantly hosted by veins in shoshonitic to high-K calc-alkaline volcanic rocks of closely similar age. Base-metal-poor, high-grade gold deposits of low sulphidation character occurring in continental sedimentary rocks of synextensional basins (e.g., Ada Tepe) show a close spatial and temporal relation to detachment faulting prior and during metamorphic core complex formation. Their formation predates local magmatism but may involve fluids from deep mantle magmas.The change in geochemical signatures of Palaeogene magmatic rocks, from predominantly silicic types in the Central Rhodopes to strongly fractionated shoshonitic (Bulgaria) to calc-alkaline and high-K calc-alkaline (Greece) magmas in the Eastern Rhodopes, coincides with the enrichment in Cu and Au relative to Pb and Zn of the associated ore deposits. This trend also correlates with a decrease in the radiogenic Pb and Sr isotope components of the magmatic rocks from west to east, reflecting a reduced crustal contamination of mantle magmas, which in turn correlates with a decreasing crustal thickness that can be observed today. Hydrogen and oxygen isotopic compositions of the related hydrothermal systems show a concomitant increase of magmatic relative to meteoric fluids, from the Pb–Zn–Ag deposits of the Central Rhodopes to the magmatic rock-hosted polymetallic gold deposits of the Eastern Rhodopes.     

Geology of massive sulphide deposits in the Spanish-Portuguese Pyrite Belt

The Spanish-Portuguese Pyrite Belt covers a large area in the SW part of the Iberian Peninsula from Seville to the westcoast of Portugal. Total reserves of aprox. 1.000 million tons of massive sulphide ores have an average content of 46% S, 42% Fe, and 2–4% Cu+Pb+Zn. The stratiform sulphide deposits and accompanying manganese mineralizations are of synsedimentary-exhalative origin. They occur in a Lower Carboniferous, geosynclinal, volcanic-sedimentary rock sequence, strongly folded during the Hercynian Orogeny. A brief outline of the regional geology of this ore province is given, and the geology of three mining districts is described: Lousal (Portugal), La Zarza and Tharsis (Huelva Province, Spain). A close relationship between sulphide and manganese ores with the submarine, acid alkaline volcanism is emphasized. Solfataric activity is responsible for the formation of sulphides in the final stages of volcanic extrusions. The ore concentration in big deposits (ore-lenses with up to 100 million tons of massive sulphides) has been due to inflows of sulphide muds and/or detrital sulphides into newly formed depressions of a contineously changing seafloor topography due to volcano tectonic movements.     

Silver and silver-bearing minerals at the Um Samiuki volcanogenic massive sulphide deposit, Eastern Desert, Egypt

The Um Samiuki Zn–Cu–Pb–Ag mineralisation, south Eastern Desert, Egypt is hosted by felsic volcanic rocks which form part of the 712-Ma-old, east-west-trending Shadli Volcanic Belt. Two major occurrences of massive sulphides are present at the top of rhyolitic breccia in the Western and Eastern mine areas. In each occurrence, a bornite-bearing zone is overlain by a pyrite-chalcopyrite-bearing zone and underlain by a disseminated, Cu-depleted zone. In the massive sulphide ore, sphalerite, chalcopyrite, pyrite, galena, bornite and tetrahedrite–tennantite are major minerals, whereas arsenopyrite, pyrrhotite, molybdenite and magnetite are accessory phases. Covellite and digenite are common secondary minerals. Bornite, tetrahedrite–tennantite and covellite contain high amounts of silver (averages of 1.97, 1.39 and 1.82 wt% respectively). Based on mineralogical balance calculations, bornite and covellite accommodate 80% of silver in the Um Samiuki deposit. Ag was incorporated in the crystal structure of the early-crystallised copper sulphides and sulphosalts and silver minerals. The temperature, sequential precipitation of the fluids and the structure of the crystallising phases control the distribution of silver. Post-depositional deformation and metamorphic processes caused liberation, remobilisation and redeposition of silver within the massive sulphides.Editorial handling: D. Lentz     

Synchronous deposition of massive sulphide deposits in the Iberian Pyrite Belt: New data from Las Herrerías and La Torerera ore-bodies

Two small to medium sized massive sulphide deposits, Las Herrerías and La Torerera, located in the Iberian Pyrite Belt (IPB) are examined from a geological and palynostratigraphic perspective. The palynological assemblages are assignable to the Retispora lepidophyta–Verrucosisporites nitidus (LN) miospore Biozone (Latest Devonian: Latest Famennian/Strunian) of Western Europe. This age permits correlation with some of the main massive sulphide deposits dated so far in the region (viz., Tharsis, Aznalcóllar, Sotiel-Coronada or Neves-Corvo), and validates once again the hypothesis that a single mineralizing event was responsible for the genesis of most of the IPB’s massive sulphide deposits. The present study confirms that palynostratigraphy is an invaluable high-resolution biostratigraphic tool in the IPB, applicable to dating, correlation and ore-exploration.     

Geochemistry and evolution of ore-forming fluids of the Yueshan Cu–Au skarn- and vein-type deposits, Anhui Province, South China

The Yueshan mineral belt is geotectonically located at the centre of the Changjiang deep fracture zone or depression of the lower Yangtze platform. Two main types of ore deposits occur in the Yueshan orefield: Cu–Au–(Fe) skarn deposits and Cu–Mo–Au–(Pb–Zn) hydrothermal vein-type deposits. Almost all deposits of economic interest are concentrated within and around the eastern and northern branches of the Yueshan dioritic intrusion. In the vicinity of the Zongpu and Wuhen intrusions, there are many Cu–Pb–Zn–Au–(S) vein-type and a few Cu–Fe–(Au) skarn-type occurrences.Fluid inclusion studies show that the ore-forming fluids are characterised by a Cl⁻(S)–Na⁺–K⁺ chemical association. Hydrothermal activity associated with the above two deposit types was related to the Yueshan intrusion. The fluid salinity was high during the mineralisation processes and the fluid also underwent boiling and mixed with meteoric water. In comparison, the hydrothermal activity related to the Zongpu and Wuhen intrusions was characterised by low salinity fluids. Chlorine and sulphur species played an important role in the transport of ore-forming components.Hydrogen- and oxygen-isotope data also suggest that the ore-forming fluids in the Yueshan mineral belt consisted of magmatic water, mixed in various proportions with meteoric water. The enrichment of ore-forming components in the magmatic waters resulted from fluid–melt partitioning. The ore fluids of magmatic origin formed large Cu–Au deposits, whereas ore fluids of mixed magmatic-meteoric origin formed small- to medium-sized deposits.The sulphur isotopic composition of the skarn- and vein-type deposits varies from − 11.3‰ to + 19.2‰ and from + 4.2‰ to + 10.0‰, respectively. These variations do not appear to have been resulted from changes of physicochemical conditions, rather due to compositional variation of sulphur at the source(s) and by water–rock interaction. Complex water–rock interaction between the ore-bearing magmatic fluids and sedimentary wall rocks was responsible for sulphur mixing. Lead and silicon isotopic compositions of the two deposit types and host rocks provide similar indications for the sources and evolution of the ore-forming fluids.Hydrodynamic calculations show that magmatic ore-forming fluids were channelled upwards into faults, fractures and porous media with velocities of 1.4 m/s, 9.8 × 10^− 1 to 9.8 × 10^− 7 m/s and 3.6 × 10^− 7 to 4.6 × 10^− 7 m/s, respectively. A decrease of fluid migration velocity in porous media or tiny fractures in the contact zones between the intrusive rocks and the Triassic sedimentary rocks led to the deposition of the ore-forming components. The major species responsible for Cu transport are deduced to have been CuCl, CuCl₂⁻, CuCl₃²⁻ and CuClOH, whereas Au was transported as Au₂(HS)₂S²⁻, Au(HS)₂⁻, AuHS and AuH₃SiO₄ complexes. Cooling and a decrease in chloride ion concentration caused by fluid boiling and mixing were the principal causes of Cu deposition. Gold deposition was related to decrease of pH, total sulphur concentration and fO₂, which resulted from fluid boiling and mixing.Geological and geochemical characteristics of the two deposit types in the Yueshan mineral belt suggest that there is a close genetic relationship with the dioritic magmatism. Geochronological data show that the magmatic activity and the mineralisation took place between 130 and 136 Ma and represent a continuous process during the Yanshanian time. The cooling of the intrusions and the mineralisation event might have lasted about 6 Ma. The cooling rate of the magmatic intrusions was 80 to 120 °C my^− 1, which permitted sufficient heat supply by magma to the ore-forming system.     

Petrographic,fluid inclusion and isotopic study of the Dikulushi Cu–Ag deposit,Katanga (D.R.C.): implications for exploration

The Dikulushi Cu–Ag vein-type deposit is located on the Kundelungu Plateau, in the southeastern part of the Democratic Republic of Congo (D.R.C.). The Kundelungu Plateau is situated to the north of the Lufilian Arc that hosts the world-class stratiform Cu–Co deposits of the Central African Copperbelt. A combined petrographic, fluid inclusion and stable isotope study revealed that the mineralisation at Dikulushi developed during two spatially and temporally distinct mineralising episodes. An early Cu–Pb–Zn–Fe mineralisation took place during the Lufilian Orogeny in a zone of crosscutting EW- and NE-oriented faults and consists of a sequence of sulphides that precipitated from moderate-temperature, saline H₂O–NaCl–CaCl₂-rich fluids. These fluids interacted extensively with the country rocks. Sulphur was probably derived from thermochemical reduction of Neoproterozoic seawater sulphate. Undeformed, post-orogenic Cu–Ag mineralisation remobilised the upper part of the Cu–Pb–Zn–Fe mineralisation in an oxidising environment along reactivated and newly formed NE-oriented faults in the eastern part of the deposit. This mineralisation is dominated by massive Ag-rich chalcocite that precipitated from low-temperature H₂O–NaCl–KCl fluids, generated by mixing of moderate- and low-saline fluids. The same evolution in mineralisation assemblages and types of mineralising fluids is observed in three other Cu deposits on the Kundelungu Plateau. Therefore, the recognition of two distinct types of (vein-type) mineralisation in the study area has a profound impact on the exploration in the Kundelungu Plateau region. The identification of a Cu–Ag type mineralisation at the surface could imply the presence of a Cu–Pb–Zn–Fe mineralisation at depth.     

Leaching of S,Cu, and Fe from disseminated Ni-(Fe)-(Cu) sulphide ore during serpentinization of dunite host rocks at Mount Keith,Agnew-Wiluna belt,Western Australia

Komatiite-hosted disseminated Ni sulphide deposits in the Agnew-Wiluna greenstone belt occur both above and below the olivine isograd that was imposed on the greenstone sequence during the M2 metamorphic/deformation event. Deposits in the northern and central part of the belt and that are located below the isograd (Mount Keith, Honeymoon Well and West Jordan) have complex sulphide mineralogy and strongly zoned sulphide assemblages. These range from least-altered assemblages of pentlandite-pyrrhotite-chalcopyrite±pyrite to altered assemblages of pentlandite±chalcopyrite, pentlandite-heazlewoodite (or millerite), heazlewoodite (or millerite), and rarely to heazlewoodite-native Ni. Deposits to the south and that are above of the olivine isograd (Six Mile, Goliath North) are dominated by less complex magmatic assemblages with a lower proportion of weakly altered pentlandite±chalcopyrite assemblages. More altered assemblages are uncommon in these deposits and occur as isolated patches around the periphery of the deposits. The sulphide zonation is reflected by whole-rock reductions in S, Cu, Fe and Zn, whereas Ni, Pt and Pd and, with some exceptions, Co are conservative. The leaching of S, Cu, Fe and Zn from sulphide assemblages and the whole rock was initiated by highly reduced conditions that were produced during low fluid/rock ratio serpentinization. Consumption of H₂O resulted in Cl, a component of the fluid, being concentrated sufficiently to stabilise iowaite as part of lizardite-rich assemblages. Once the rate of olivine hydration reactions declined and during and after expansion and associated fracturing of the ultramafic sequence allowed higher fluid access, a more fluid-dominated environment formed and new carbonate-bearing fluid gained access to varying extents to the ultramafic rock sequence. This drove Cl from iowaite (to form pyroaurite) and caused the sulphide assemblages to be altered from the original magmatic assemblages and compositions to those stable at the prevailing fO₂ and fS₂ conditions. Mass transfer was made possible via metal chloride complexes and H₂S with fluids driven by deformation associated with the M2 metamorphism. Disseminated deposits in higher metamorphic grade terrains where olivine was stable during peak metamorphism did not undergo the metasomatism seen in the deposits in areas of lower metamorphic grade. Some minor leaching of S, Fe and Cu occurred around the periphery of the deposits during early, pre-M2 peak metamorphism, but once olivine stability was reached the driving force for the series of leaching reactions was exhausted. The effect of this process on the original magmatic sulphides is to induce significant variability in texture, mineralogy and bulk composition and to markedly reduce the Fe and S contents of the sulphide fraction (in extreme cases to zero for both elements), and to reduce the volume of the sulphide fraction per unit of Ni. These changes impact unfavourably on Ni sulphide recoveries and metallurgical characteristics of these Ni ores.     

Formation of the Wiesloch Mississippi Valley-type Zn-Pb-Ag deposit in the extensional setting of the Upper Rhinegraben, SW Germany

The Mississippi Valley-type (MVT) Zn–Pb–Ag deposit in the Wiesloch area, Southwest Germany, is controlled by graben-related faults of the Upper Rhinegraben. Mineralization occurs as vein fillings and irregular replacement ore bodies consisting of sphalerite, banded sphalerite, galena, pyrite, sulfosalts (jordanite and geocronite), barite, and calcite in the Middle Triassic carbonate host rock. Combining paragenetic information, fluid inclusion investigations, stable isotope and mineral chemistry with thermodynamic modeling, we have derived a model for the formation of the Wiesloch deposit. This model involves fluid mixing between ascending hot brines (originating in the crystalline basement) with sedimentary formation waters. The ascending brines originally had a near-neutral pH (around 6) and intermediate oxidation state, reflecting equilibrium with granites and gneisses in the basement. During fluid ascent and cooling, the pH of the brine shifted towards more acidic (around 4) and the oxidation state increased to conditions above the hematite-magnetite buffer. These chemical characteristics contrast strongly with those of the pore and fracture fluid residing in the limestone aquifer, which had a pH between 8 and 9 in equilibrium with calcite and was rather reduced due to the presence of organic matter in the limestone. Mixing between these two fluids resulted in a strong decrease in the solubility of silver-bearing sphalerite and galena, and calcite. Besides Wiesloch, several Pb–Zn deposits are known along the Upper Rhinegraben, including hydrothermal vein-type deposits like Badenweiler and the Michael mine near Lahr. They all share the same fluid origin and formation process and only differ in details of their host rock and fluid cooling paths. The mechanism of fluid mixing also seems to be responsible for the formation of other MVT deposits in Europe (e.g., Réocin, Northern Spain; Trèves, Southern France; and Cracow-Silesia, Poland), which show notable similarities in terms of their age, mineralogy. and mineral chemistry to the MVT deposit near Wiesloch.