Sulfur, lead and helium isotopic compositions of sulfide minerals from the Dachang Sn-polymetallic ore district in South China: implication for ore genesis

Summary The Dachang Sn-polymetallic ore district is one of the largest tin producing districts in China. Its origin has long been in dispute between magmatic-hydrothermal replacement and submarine exhalative-hydrothermal origin. The Dachang ore district comprises several types of ore deposits, including the Lamo magmatogenic skarn deposit near a granite intrusion, the Changpo-Tongkeng bedded and vein-type sulfide deposit, and the Gaofeng massive sulfide deposit. Sulfide minerals from the Lamo skarn ores show δ³⁴S values in the range between −3 and +4‰ with a mean close to zero, suggesting a major magmatic sulfur source that likely was the intrusive Longxianggai granite. Sulfide minerals from the Gaofeng massive ores show higher δ³⁴S values between +5 and +12‰, whereas sulfide minerals from the Changpo-Tongkeng bedded ores display lighter δ³⁴S values between −7 and −0.2‰. The difference in the sulfur isotope ranges in the two deposits can be interpreted by different degrees of inorganic thermochemcial reduction of marine sulfate using a one-step batch separation fractionation model. Sulfur isotopic compositions from the vein-type ores at Changpo-Tongkeng vary widely from −8 to +4‰, but most of the data cluster around −2.9‰, which is close to that of bedded ores (−3.6‰). The sulfur in vein-type ores might be derived from bedded ores or it represents a mixture of magmatic- and sedimentary-derived sulfur. Pb isotopic compositions of sulfide minerals in the Dachang ore district reveal a difference between massive and bedded ores, with the massive ores displaying more radiogenic Pb isotope ratios. Correlations of ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb or ²⁰⁸Pb/²⁰⁴Pb for the massive and bedded ores are interpreted as two-component mixing of Pb leached from sedimentary host rocks and from deep-seated Precambrian basement rocks composed of metamorphosed volcano-sedimentary rocks. Pb isotopic compositions of sulfide minerals from vein-type ores overlap with those of bedded sulfides. Similar to the sulfur, the lead in vein-type ores might be derived from bedded ores. Skarn ores at Lamo show very limited variations in Pb isotopic compositions, which may reflect a major magmatic-hydrothermal lead source. Helium isotope data of fluid inclusions trapped in sulfides indicate that He in the massive and bedded ores has a different origin than He in fluorite of granite-related veins. The ³He/⁴He ratios of 1.2–2.9 Ra of fluid inclusions from sulfides at Gaofeng and Changpo-Tongkeng imply a contribution of mantle-derived fluids. Overall our data support a submarine exhalative-hydrothermal origin for the massive and bedded ore types at Dachang. Supplementary material to this paper is available in electronic form at Appendix available as electronic supplementary material     

Chemical and mineralogical heterogeneity in the basal zone of the Partridge River Intrusion: implications for the origin of Cu–Ni sulfide mineralization in the Duluth Complex,midcontinent rift system

Copper–nickel sulfide mineralization in the Partridge River Intrusion of the 1.1 Ga Duluth Complex is restricted primarily to a 100 m thick zone near the base of the intrusion, which is heterogeneous at meter scales in terms of both sulfide contents and rock types, which include dunite, melatroctolite, troctolite, leucotroctolite, gabbro, olivine gabbro, gabbronorite, and rare norite. Olivine-rich troctolites and melatroctolites appear to have required mineral accumulation on a substrate, whereas augite troctolite and gabbros are thought to have formed via in situ crystallization of magmas ranging in composition from high-Al olivine tholeiite to high-Ti tholeiite. δ¹⁸O values of orthopyroxene-poor rocks in the Partridge River Intrusion range from 5.2 to 6.7‰. δ¹⁸O values of 6.7‰ are consistent with less than 20% contamination by high-¹⁸O metasedimentary country rock, either via devolatilization or local partial melting. Rocks with greater than ∼15% orthopyroxene, gabbronorites, and norites, are characterized by δ¹⁸O values in excess of 6.9‰, and required the assimilation of larger amounts of siliceous country rocks. Sulfur isotopic values in leucotroctolitic rocks that contain less than ∼400 ppm S and that overlie the basal zone range between −1.5 and 2‰, values that are consistent with those of mantle-derived sulfur. In contrast, δ³⁴S values in the basal zone range from −1.4 to 10.5‰, where the ³⁴S-enriched samples require an input of sulfur from metasedimentary country rocks. δ³⁴S values of the rocks in the basal zone correlate with variations in olivine Fo content but not with S abundance. The wide range in δ³⁴S values of rocks in the basal zone strongly suggests that magmas interacted with layers in the sedimentary country rocks that were themselves characterized by variable sulfide contents and δ³⁴S values. The S isotopic data suggest that the heterogeneity observed in the basal zone results from the emplacement of relatively thin sheets of compositionally distinct magma. All rock types present in the basal zone can be produced as a result of variable degrees of fractionation of a parental high-Al olivine tholeiite, followed by varying degrees of contamination of derivative liquids by country rocks. The S-contamination process was essential for the development of Cu–Ni mineralization, and was restricted to the earliest stages in the development of the Duluth Complex at a time when volatile species such as S and H₂O, and low-T partial melts of country rocks, were available to magmas. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

Sulfur isotope characteristics of metamorphosed Zn–Cu volcanogenic massive sulfides in the Areachap Group, Northern Cape Province, South Africa

Zn- and Cu-rich massive sulfide ores of volcanogenic origin [volcanogenic massive sulfide (VMS) deposits] occur as stratiform/stratabound lenses of variable size hosted by gneisses, amphibolites, and schists of the Areachap Group, in the Northern Cape Province of South Africa. The Areachap Group represents the highly deformed and metamorphosed remnants of a Mesoproterozoic volcanic arc that was accreted onto the western margin of the Kaapvaal Craton during the ∼1.0–1.2 Ga Namaquan Orogeny. Sulfur isotope data (δ³⁴S) are presented for 57 sulfide separates and one barite sample from five massive sulfide occurrences in the Areachap Group. Although sulfides from each site have distinct sulfur isotope values, all δ³⁴S values fall within a very limited range (3.0‰ to 8.5‰). Barite has a δ³⁴S value of 18.5‰, very different from that of associated sulfides. At one of the studied sites (Kantienpan), a distinct increase in δ³⁴S of sulfides is observed from the massive sulfide lens into the disseminated sulfides associated with a distinct footwall alteration zone. Sulfide–sulfide and sulfide–barite mineral pairs which recrystallized together during amphibolite- and lower granulite facies metamorphism are not in isotopic equilibrium. Sulfur isotope characteristics of sulfides and sulfates of the Zn–Cu ores in the Areachap Group are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and unsedimented mid-ocean ridges. It is thus concluded that profound recrystallization and textural reconstitution associated with high-grade regional metamorphism of the massive sulfide ores of the Areachap Group did not result in extensive sulfur isotopic homogenization. This is similar to observations in other metamorphosed VMS deposit districts and confirms that massive sulfide ores remain effectively a closed system for sulfur isotopes for both sulfides and sulfates during metamorphism.     

Geology,fluid inclusion and sulphur isotope characteristics of the El Cobre VHMS deposit,Southern Cuba

The El Cobre deposit is located in eastern Cuba within the volcanosedimentary sequence of the Sierra Maestra Paleogene arc. The deposit is hosted by tholeiitic basalts, andesites and tuffs and comprises thick stratiform barite and anhydrite bodies, three stratabound disseminated up to massive sulphide bodies produced by silicification and sulphidation of limestones or sulphates, an anhydrite stockwork and a siliceous stockwork, grading downwards to quartz veins. Sulphides are mainly pyrite, chalcopyrite and sphalerite; gold occurs in the stratabound ores. Fluid inclusions measured in sphalerite, quartz, anhydrite and calcite show salinities between 2.3 and 5.7 wt% NaCl eq. and homogenisation temperatures between 177 and 300°C. Sulphides from the stratabound mineralisation display δ ³⁴S values of 0‰ to +6.0‰, whilst those from the feeder zone lie between −1.4‰ and +7.3‰. Sulphides show an intra-grain sulphur isotope zonation of about 2‰; usually, δ ³⁴S values increase towards the rims. Sulphate sulphur has δ ³⁴S in the range of +17‰ to +21‰, except two samples with values of +5.9‰ and +7.7‰. Sulphur isotope data indicate that the thermochemical reduction of sulphate from a hydrothermal fluid of seawater origin was the main source of sulphide sulphur and that most of the sulphates precipitated by heating of seawater. The structure of the deposit, mineralogy, fluid inclusion and isotope data suggest that the deposit formed from seawater-derived fluids with probably minor supply of magmatic fluids.     

Sulfur isotope characteristics of the Archean Cu–Zn Gossan Hill VHMS deposit, Western Australia

Gossan Hill is an Archean (∼3.0 Ga) Cu–Zn–magnetite-rich volcanic-hosted massive sulfide (VHMS) deposit in the Yilgarn Craton of Western Australia. Massive sulfide and magnetite occur within a layered succession of tuffaceous, felsic volcaniclastic rocks of the Golden Grove Formation. The Gossan Hill deposit consists of two stratigraphically separate ore zones that are stratabound and interconnected by sulfide veins. Thickly developed massive sulfide and stockwork zones in the north of the deposit are interpreted to represent a feeder zone. The deposit is broadly zoned from a Cu–Fe-rich lower ore zone, upwards through Cu–Zn to Zn–Ag–Au–Pb enrichment in the upper ore zone. New sulfur isotope studies at the Gossan Hill deposit indicate that the variation is wider than previously reported, with sulfide δ³⁴S values varying between −1.6 and 7.8‰ with an average of 2.1 ± 1.4‰ (1σ error). Sulfur isotope values have a broad systematic stratigraphic increase of approximately 1.2‰ from the base to the top of the deposit. This variation in sulfur isotope values is significant in view of typical narrow ranges for Archean VHMS deposits. Copper-rich sulfides in the lower ore zone have a narrower range (δ³⁴S values of −1.6 to 3.4‰, average ∼1.6 ± 0.9‰) than sulfides in the upper ore zone. The lower ore zone is interpreted to have formed from a relatively uniform reduced sulfur source dominated by leached igneous rock sulfur and minor magmatic sulfur. Towards the upper Zn-rich ore zone, an overall increase in δ³⁴S values is accompanied by a wider range of δ³⁴S values, with the greatest variation occurring in massive pyrite at the southern margin of the upper ore zone (−1.0 to 7.8‰). The higher average δ³⁴S values (2.8 ± 2.1‰) and their wider range are explained by mixing of hydrothermal fluids containing leached igneous rock sulfur with Archean seawater (δ³⁴S values of 2 to 3‰) near the paleoseafloor. The widest range of δ³⁴S values at the southern margin of the deposit occurs away from the feeder zone and is attributed to greater seawater mixing away from the central upflow zone. Received: 10 June 1999 / Accepted: 28 December 1999     

Genesis of sediment-hosted stratiform copper–cobalt mineralization at Luiswishi and Kamoto, Katanga Copperbelt (Democratic Republic of Congo)

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 ∆³⁴S_SO4-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.     

Isotopic constraints on fluid evolution and precipitation mechanisms for the Boléo Cu–Co–Zn district, Mexico

Stable and radiogenic isotope composition of stratiform Cu–Co–Zn mineralization and associated sedimentary rocks within the Boléo district of the Miocene Santa Rosalía basin, Baja California Sur, constrains the evolution of seawater and hydrothermal fluids and the mechanisms responsible for sulfide and oxide deposition. Stable isotope geochemistry of limestone and evaporite units indicates a strong paleogeographic influence on the chemistry of the water column. Near-shore limestone at the base of the Boléo Formation is characterized by modified marine carbon (δ ¹³C_PDB=−6.0 to +4.4‰) and oxygen (δ ¹⁸O_SMOW=+19.5 to +26.2‰) isotope composition due to the influx of ¹³C- and ¹⁸O-depleted fluvial water. Sulfate sulfur isotope composition (δ ³⁴S_CDT=+17.21 to +22.3‰ and δ ¹⁸O_SMOW=+10.7 to +13.1‰) for basal evaporite and claystone facies are similar to Miocene seawater. Strontium isotopes are less radiogenic than expected for Miocene seawater due to interaction with volcanic rocks. Low S/C ratios, high Mn contents and sedimentological evidence indicate the basin water column was oxidizing. The oxygenated basin restricted sulfide precipitation to within the sedimentary pile by replacement of early diagenetic framboidal pyrite and pore-space filling by Cu–Co–Zn sulfides to produce disseminated sulfides. Quartz–Mn oxide oxygen isotope geothermometry constrains mineralization temperature between 18 and 118°C. Sulfur isotopes indicate the following sources of sulfide: (1) bacterial sulfate reduction within the sedimentary pile produced negative δ ³⁴S values (<−20‰) in framboidal pyrite; and (2) bacterial sulfate reduction at high temperature (80–118°C) within the sedimentary pile during the infiltration of the metal-bearing brines produced Cu–Co–Zn sulfides with negative, but close to 0‰, δ ³⁴S values. Isotope modeling of fluid-rock reaction and fluid mixing indicates: (1) sedimentary and marine carbonates (δ ¹³C=−11.6 to −3.2‰ and δ ¹⁸O=+19.0 to +21.8‰) precipitated from basin seawater/pore water that variably mixed with isotopically depleted meteoric waters; and (2) hydrothermal calcite (δ ¹³C=−7.9 to +4.3‰ and δ ¹⁸O=+22.1 to +25.8‰) formed by dissolution and replacement of authigenic marine calcite by downward-infiltrating metalliferous brine and brine-sediment exchange, that prior to reaction with calcite, had mixed with isotopically depleted pore water. The downward infiltration of metalliferous brine is inferred from lateral and stratigraphic metal distributions and from the concentration of Cu sulfides along the upper contact of pyrite-bearing laminae. The co-existence and textural relationships among framboidal pyrite, base metal sulfides, carbonate and Mn–Fe oxides (including magnetite) within mineralized units are consistent with carbonate replacement and high-temperature bacterial reduction within the sedimentary pile occurring simultaneously below a seawater column under predominantly oxygenated conditions.     

Sulfur isotopic systematics of granitoids from southwestern New Brunswick, Canada: implications for magmatic-hydrothermal processes, redox conditions, and gold mineralization

Bulk δ ³⁴S_rock 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 ³⁴S_rock value of the whole-rock sample and the δ ³⁴S_sulfide (or δ ³⁴S_sulfate) 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.     

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ³⁴S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.     

Metallogeny of the Mont-de-l’Aigle IOCG deposit, Gaspé Peninsula, Québec, Canada

The Mont-de-l’Aigle deposit is located in the northern part of Dome Lemieux, in the Connecticut Valley-Gaspé Synclinorium, Gaspé Peninsula, Québec. The Dome Lemieux is a subcircular antiform of Siluro–Devonian sedimentary rocks that is cut by numerous mafic and felsic sills and dikes of Silurian to Late Devonian age. Plutonism occurred in a continental within-plate extensional setting typical of orogenic collapse. The Cu−Fe (± Au) mineralization of Mont-de-l’Aigle occurs in veins, stockworks, and breccias. Mineralization is located near or within N−S and NW−SE faults cutting sedimentary rocks. IOCG mineralization postdates intrusions, skarns, hornfels, and epithermal mineralization typical of the southern part of the Dome Lemieux. The paragenetic sequence comprises: (1) pervasive sodic, potassic, chlorite, and silica alteration, (2) hematite, quartz, pyrite, magnetite, and chalcopyrite veins, stockworks and breccias and, (3) dolomite ± hematite veins and veinlets cutting the earlier mineralization. Intrusions display proximal sodic and potassic alteration, whereas sedimentary rocks have proximal decalcification, silicification, and potassic alteration. Both intrusive and sedimentary rocks are affected by a pervasive distal chlorite (± silica) alteration. The sulfur isotope composition of pyrite and chalcopyrite (δ³⁴S=−1.5 to 4.8‰) suggests that sulfur was derived mainly from igneous rocks. Fluid δ¹⁸O (−0.4 to 2.65‰) indicates meteoric or seawater that reacted with the country rocks. Mixing of hot magmatic fluids with a cooler fluid, perhaps meteoric or seawater is suggested for mineral deposition and alteration of the Mont-de-l’Aigle deposit. The mineralogy, alteration, and sulfur isotope composition of the Mont-de-l’Aigle deposit compare well with IOCG deposits worldwide, making the Mont-de-l’Aigle deposit a rare example of Paleozoic IOCG mineralization, formed at shallow depth, within a low metamorphic grade sedimentary rock sequence.     

Sulfur isotope variations from orebody to hand-specimen scale at the Mežica lead–zinc deposit, Slovenia: a predominantly biogenic pattern

The Mississippi Valley-type (MVT) Pb–Zn ore district at Mežica is hosted by Middle to Upper Triassic platform carbonate rocks in the Northern Karavanke/Drau Range geotectonic units of the Eastern Alps, northeastern Slovenia. The mineralization at Mežica covers an area of 64 km² with more than 350 orebodies and numerous galena and sphalerite occurrences, which formed epigenetically, both conformable and discordant to bedding. While knowledge on the style of mineralization has grown considerably, the origin of discordant mineralization is still debated. Sulfur stable isotope analyses of 149 sulfide samples from the different types of orebodies provide new insights on the genesis of these mineralizations and their relationship. Over the whole mining district, sphalerite and galena have δ ³⁴ S values in the range of –24.7 to –1.5‰ VCDT (–13.5 ± 5.0‰) and –24.7 to –1.4‰ (–10.7 ± 5.9‰), respectively. These values are in the range of the main MVT deposits of the Drau Range. All sulfide δ ³⁴ S values are negative within a broad range, with δ ³⁴ S _pyrite <δ ³⁴ S _sphalerite <δ ³⁴ S _galena for both conformable and discordant orebodies, indicating isotopically heterogeneous H₂S in the ore-forming fluids and precipitation of the sulfides at thermodynamic disequilibrium. This clearly supports that the main sulfide sulfur originates from bacterially mediated reduction (BSR) of Middle to Upper Triassic seawater sulfate or evaporite sulfate. Thermochemical sulfate reduction (TSR) by organic compounds contributed a minor amount of ³⁴S-enriched H₂S to the ore fluid. The variations of δ ³⁴ S values of galena and coarse-grained sphalerite at orefield scale are generally larger than the differences observed in single hand specimens. The progressively more negative δ ³⁴ S values with time along the different sphalerite generations are consistent with mixing of different H₂S sources, with a decreasing contribution of H₂S from regional TSR, and an increase from a local H₂S reservoir produced by BSR (i.e., sedimentary biogenic pyrite, organo-sulfur compounds). Galena in discordant ore (–11.9 to –1.7‰; –7.0 ± 2.7‰, n = 12) tends to be depleted in ³⁴ S compared with conformable ore (–24.7 to –2.8‰, –11.7 ± 6.2‰, n = 39). A similar trend is observed from fine-crystalline sphalerite I to coarse open-space filling sphalerite II. Some variation of the sulfide δ ³⁴ S values is attributed to the inherent variability of bacterial sulfate reduction, including metabolic recycling in a locally partially closed system and contribution of H₂S from hydrolysis of biogenic pyrite and thermal cracking of organo-sulfur compounds. The results suggest that the conformable orebodies originated by mixing of hydrothermal saline metal-rich fluid with H₂S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralization.     

Evidence for metallogenic geochemistry of volcano-hot spring deposition in Xiqiu copper deposit, Zhejiang Province, China

There were strong volcanic and hot spring activities in Late proterozic in the Xiqiu mining district,Zhejiang province,The volcanic rocks and hydrothermal sedimentary cherts have high contents of the major metallogenic elements,Their atomic percentage of Cu:Zn:Pb is similar very much between volcanic rock,hydrothermal sedimentary chert and ore.Therefore,the metallization has a direct bearing on the volcanic and hot spring activities in the Xiqiu area.The δ34S values vary from -6.5‰to 2.8‰,the δ30Si Values from-0.2‰ to 0.6‰,and the δ18O Values from 8.14‰ to 22.32‰,Lead isotopes were derived mainly from the lower crust.The ores have high contents of As,Sb,Bi,Ga,Zn,and Ba,and low Al/(Al Fe Mn)ratios,with Zn/(Zn Pb)ratios approximate to unity,Therefore,the Xiqiu massive copper sulfide deposit can be ascribed to volcano-hot spring deposition.     

S,Pb, C and O isotopic compositions and ore genesis of the strata-bound polymetallic sulfide deposits in central Inner Mongolia,China

The strata-bound Cu−Pb−Zn polymetallic sulfide deposits occur in metamorphic rocks of greenschist phase of the middle-upper Proterozoic Langshan Group in central Inner Mongolia. δ³⁴S values for sulfides range from −3.1‰ to +37.3‰, and an apparent difference is noticed between vein sulfides and those in bedded rocks. For example, δ³⁴S values for bedded pyrite range from +10.6‰ to +20.0‰, while those for vein pyrite vary from −3.1‰ to +14.1‰. δ³⁴S of bedded pyrrhotite is in the range +7.9‰–+23.5‰ in comparison with +6.5‰–+17.1‰ for vein pyrrhotite. The wide scatter of δ³⁴S and the enrichment of heavier sulfur indicate that sulfur may have been derived from H₂S as a result of bacterial reduction of sulfates in the sea water. Sulfur isotopic composition also differs from deposit to deposit in this area because of the difference in environment in which they were formed. The mobilization of bedded sulfides in response to regional metamorphism and magmatic intrusion led to the formation of vein sulfides. δ¹⁸O and δ¹³C of ore-bearing rocks and wall rocks are within the range typical of ordinary marine facies, with the exception of lower values for ore-bearing marble at Huogeqi probably due to diopsidization and tremalitization of carbonate rocks. Pb isotopic composition is relatively stable and characterized by lower radio-genetic lead. The age of basement rocks was calculated to be about 23.9 Ma and ore-forming age 7.8 Ma.²⁰⁷Pb/²⁰⁴Pb−²⁰⁶Pb/²⁰⁴Pb and²⁰⁸Pb/²⁰⁴Pb−²⁰⁶Pb/²⁰⁴Pb plots indicate that Pb may probably be derived from the lower crust or upper mantle. It is believed that the deposits in this region are related to submarine volcanic exhalation superimposed by later regional metamorphism and magmatic intrusion.     

Geochemistry of bedded barite of the Mesoproterozoic Aggeneys-Gamsberg Broken Hill-type district,South Africa

Stratiform and stratabound barite ± magnetite beds are intimately associated with the polymetallic Broken Hill-type (BHT) massive sulfide deposits of the Aggeneys-Gamsberg Pb–Zn–Cu ± Ag–Ba district in the Northern Cape Province, South Africa. Barite samples were collected and studied from four localities in the district. Although metamorphic water–rock interaction processes have partially altered the chemical and to a lesser degree the isotopic composition of barite, samples identified as being the least altered display distinctly different isotopic compositions that are thought to reflect different modes of origin. All barite samples are marked by low concentrations of SrO (0.5 ± 0.2 wt%), highly radiogenic ⁸⁷Sr/⁸⁶Sr ratios, elevated δ ³⁴S and δ ¹⁸O values compared to contemporaneous Mesoproterozoic seawater. Radiogenic ⁸⁷Sr/⁸⁶Sr signatures (0.7164 ± 0.0028) point to an evolved continental crustal source for Sr and Ba, while elevated δ ³⁴S values (27.3 ± 4.9‰) indicate that contemporaneous seawater sulfate, modified by bacterial sulfate reduction, was the single most important sulfur reservoir for barite deposition. Most importantly, δ ¹⁸O values suggest a lower temperature of formation for the Gamsberg deposit compared with the occurrences in the Aggeneys area, i.e. Swartberg-Tank Hill and Big Syncline. The obvious differences in temperature of formation are in good agreement with the Cu-rich, Ba-poor nature of the sulfide mineralization of the Aggeneys deposits vs the Cu-poor, Ba-rich character of the Gamsberg deposit. In conjunction with this, isotopic and petrographic arguments favor a sub-seafloor replacement model for the stratabound barite occurrences of the Aggeneys deposits, while at Gamsberg, deposition at the sediment–water interface as a true sedimentary exhalite appears more likely.     

Geology and vein tin mineralization in the Dadoushan deposit,Gejiu district,SW China

Vein-type tin mineralization in the Dadoushan deposit, Laochang ore field, Gejiu district, SW China, is predominantly hosted in Triassic carbonate rocks (Gejiu Formation) over cupolas of the unexposed Laochang equigranular granite intrusion. The most common vein mineral is tourmaline, accompanied by skarn minerals (garnet, diopside, epidote, phlogopite) and beryl. The main ore mineral is cassiterite, accompanied by minor chalcopyrite, pyrrhotite, and pyrite, as well as scheelite. The tin ore grade varies with depth, with the highest grades (~1.2 % Sn) prevalent in the lower part of the vein zone. Muscovite ⁴⁰Ar–³⁹Ar dating yielded a plateau age of 82.7 ± 0.7 Ma which defines the age of the vein-type mineralization. Measured sulfur isotope compositions (δ ³⁴S = −4.1 to 3.9 ‰) of the sulfides (arsenopyrite, chalcopyrite, pyrite, and pyrrhotite) indicate that the sulfur in veins is mainly derived from a magmatic source. The sulfur isotope values of the ores are consistent with those from the underlying granite (Laochang equigranular granite, −3.7 to 0.1 ‰) but are different from the carbonate wall rocks of the Gejiu Formation (7.1 to 11.1 ‰). The calculated and measured oxygen and hydrogen isotope compositions of the ore-forming fluids (δ ¹⁸O_H2O = −2.4 to 5.5 ‰, δD = −86 to −77 ‰) suggest an initially magmatic fluid which gradually evolved towards meteoric water during tin mineralization.     

Evidence for a magmatic origin for Carlin-type gold deposits: isotopic composition of sulfur in the Betze-Post-Screamer Deposit, Nevada, USA

We report here new sulfur isotope analyses from the Betze-Post-Screamer deposit, the largest Carlin-type gold deposit in the world. Carlin-type deposits contain high concentrations of arsenic, antimony, mercury, tellurium and other elements of environmental interest, and are surrounded by large volumes of crust in which these elements are also enriched. Uncertainty about the source of sulfur and metals in and around Carlin-type deposits has hampered formulation of models for their origin, which are needed for improved mineral exploration and environmental assessment. Previous studies have concluded that most Carlin-type deposits formed from sulfide sulfur that is largely of sedimentary origin. Most of these studies are based on analyses of mineral separates consisting of pre-ore diagenetic pyrite with thin overgrowths of ore-related arsenian pyrite rather than pure, ore-related pyrite. Our SIMS spot analyses of ore-related pyrite overgrowths in the Screamer zone of the Betze-Post-Screamer deposit yield δ³⁴S values of about −1 to 4‰ with one value of about 7‰. Conventional analyses of realgar and orpiment separates from throughout the deposit yield δ³⁴S values of about 5–7‰ with one value of 10‰ in the Screamer zone. These results, along with results from an earlier SIMS study in the Post zone of the deposit and phase equilibrium constraints, indicate that early arsenian pyrite were formed from fluids of magmatic origin with variable contamination from sulfur in Paleozoic sedimentary rocks. Later arsenic sulfides were formed from solutions to which sulfur of sedimentary origin had been added. The presence of Paleozoic sedimentary sulfur in Carlin-type deposits does not require direct involvement of hydrothermal solutions of sedimentary origin. Instead, it could have been added by magmatic assimilation of Paleozoic sedimentary rocks or by hydrothermal leaching of sulfur from wall rocks to the deposit. Thus, the dominant process delivering sulfur, arsenic, gold and mineralizing fluids to Carlin-type systems and their surrounding country rocks was probably separation of fluids from a magmatic source. Editorial handling: G. Beaudoin     

Origin of the Nchanga copper–cobalt deposits of the Zambian Copperbelt

The Zambian Copperbelt forms the southeastern part of the 900-km-long Neoproterozoic Lufilian Arc and contains one of the world’s largest accumulations of sediment-hosted stratiform copper mineralization. The Nchanga deposit is one of the most significant ore systems in the Zambian Copperbelt and contains two major economic concentrations of copper and cobalt, hosted within the Lower Roan Group of the Katangan Supergroup. A Lower Orebody (copper only) and Upper Orebody (copper and cobalt) occur towards the top of arkosic units and within the base of overlying shales. The sulfide mineralogy includes pyrite, bornite, chalcopyrite, and chalcocite, although in the Lower Orebody, sulfide phases are partially or completely replaced by malachite and copper oxides. Carrollite is the major cobalt-bearing phase and is restricted to fault-propagation fold zones within a feldspathic arenite. Hydrothermal alteration minerals include dolomite, phlogophite, sericite, rutile, quartz, tourmaline, and chlorite. Quartz veins from the mine sequence show halite-saturated fluid inclusions, ranging from ~31 to 38 wt% equivalent NaCl, with homogenisation temperatures (Th_TOT) ranging between 140 and 180°C. Diagenetic pyrites in the lower orebody show distinct, relatively low δ ³⁴S, ranging from −1 to −17‰ whereas arenite- and shale-hosted copper and cobalt sulfides reveal distinctly different δ ³⁴S from −1 to +12‰ for the Lower Orebody and +5 to +18‰ for the Upper Orebody. There is also a clear distinction between the δ ³⁴S mean of +12.1±3.3‰ (n=65) for the Upper Orebody compared with +5.2±3.6‰ (n=23) for the Lower Orebody. The δ ¹³C of dolomites from units above the Upper Orebody give δ ¹³C values of +1.4 to +2.5‰ consistent with marine carbon. However, dolomite from the shear-zones and the alteration assemblages within the Upper Orebody show more negative δ ¹³C values: −2.9 to −4.0‰ and −5.6 to −8.3‰, respectively. Similarly, shear zone and Upper Orebody dolomites give a δ ¹⁸O of +11.7 to +16.9‰ compared to Lower Roan Dolomites, which show δ ¹⁸O of +22.4 to +23.0‰_. Two distinct structural regimes are recognized in the Nchanga area: a weakly deformed zone consisting of basement and overlying footwall siliciclastics, and a moderate to tightly folded zone of meta-sediments of the Katangan succession. The fold geometry of the Lower Roan package is controlled by internal thrust fault-propagation folds, which detach at the top of the lowermost arkose or within the base of the overlying stratigraphy and show vergence towards the NE. Faulting and folding are considered to be synchronous, as folding predominantly occurred at the tips of propagating thrust faults, with local thrust breakthrough. The data from Nchanga suggests a strong link between ore formation and the development of structures during basin inversion as part of the Lufilian Orogeny. Sulfides tend to be concentrated within arenites or coarser-grained layers within shale units, suggesting that host-rock porosity and possibly permeability played a role in ore formation. However, sulfides are also commonly orientated along, but not deformed by, a tectonic fabric or hosted within small fractures that suggest a significant role for deformation in the development of the mineralization. The ore mineralogy, hydrothermal alteration, and stable isotope data lend support to models consistent with the thermochemical reduction of a sulfate- (and metal) enriched hydrothermal fluid, at the site of mineralization. There is no evidence at Nchanga for a contribution of bacteriogenic sulfide, produced during sedimentation or early diagenesis, to the ores.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.Editorial handling: H. Frimmel     

Stable isotope geochemistry and diagenetic mineralization associated with the Tono sandstone-type uranium deposit in Japan

The Tono sandstone-type uranium mine area, middle Honsyu, Japan is composed of Miocene lacustrine sedimentary rocks in the lower part (18–22 Ma) and marine facies in the upper part (15–16 Ma). Calcite and pyrite occur as dominant diagenetic alteration products in these Neogene sedimentary rocks. The characteristics of calcite and pyrite differ significantly between lacustrine and marine facies. Abundant pyrite, calcite, organic matter, and small amounts of marcasite or pyrrhotite occur in the lacustrine facies, whereas small amounts of calcite and framboidal pyrite, organic matter and no marcasite or pyrrhotite are found within the marine units. The δ¹³C values of calcite in the lacustrine deposits are low (−19 to −6‰ PDB) but those in marine formation are high (−11 to +3‰). This implies that the contribution of marine carbonate is larger in upper marine sedimentary rocks, and carbon in calcite in the lower lacustrine formation was derived both from oxidation of organic matter and from dissolved marine inorganic carbon. The δ³⁴S values of framboidal pyrite in the upper marine formation are low (−14 to −8‰ CDT), indicating a small extent of bacterial seawater sulfate reduction, whereas those of euhedral-subhedral pyrite in the lower lignite-bearing arkose sandstone are high (+10 to +43‰), implying a large extent of closed-system bacterial seawater sulfate reduction. The δ³⁴S and δ¹³C data which deviate from a negative correlation line toward higher δ¹³C values suggest methanogenic CO₂ production. During diagenesis of the lacustrine unit, large amounts of euhedral-subhedral pyrite were formed, facilitated by extensive bacterial reduction of seawater sulfate with concomitant oxidation of organic matter, and by hydrolysis reactions of organic matter, producing CH₄ and CO₂. Uranium minerals (coffinite and uraninite) were also formed at this stage by the reduction of U⁶⁺ to U⁴⁺. The conditions of diagenetic alteration within the lacustrine deposits and uranium mineralization is characterized by low Eh in which nearly equal concentrations of CH₄ and HCO₃ ⁻ existed and reduced sulfur species (H₂S, HS⁻) are predominant among aqueous sulfur species, whereas diagenetic alteration of the marine formations was characterized by a predominance of SO₄ ²⁻ among dissolved sulfur species. Modern groundwater in the lacustrine formation has a low Eh value (−335 mV). Estimated and measured low Eh values of modern and ancient interstitial waters in lacustrine environments indicate that a reducing environment in which U⁴⁺ is stable has been maintained since precipitation of uranium minerals. Received: 9 February 1996 / Accepted: 11 April 1997     

Oxygen isotopic composition of quartz veins and host rocks at the Sukhoi Log deposit,Russia

The relationships between the δ¹⁸O of quartz veins and veinlets pertaining to the main stage of gold mineralization at the Sukhoi Log deposit and metasomatically altered host slates are estimated. The oxygen isotopic composition of veined quartz and host slates is not uniform. The δ¹⁸O of quartz veins from the Western, Central, and Sukhoi Log areas of the deposit vary from +16 to + 18 ‰. The δ¹⁸O range of metasomatically altered slates in the Western and Sukhoi Log areas attains 6 ‰. The δ¹⁸O of quartz veins are always higher than those of host slates by 3–7‰. The regular difference in the δ¹⁸O between quartz veins and host slates indicates that the oxygen isotopic composition of the ore-bearing fluid forming the system of quartz veins and veinlets at the Sukhoi Log deposit could have formed as a result of interaction with silicate rocks, for instance, terrigenous slates enriched in δ¹⁸O. Such interaction, however, took place at deeper levels of the Sukhoi Log deposit. It is suggested that the fluid phase participating in the formation of the vein and veinlet system had initially high δ¹⁸O(>+10‰) due to interaction with the rocks enriched in δ¹⁸O at a low fluid/rock ratio. The oxygen isotope data indicate that the fluid participating in the formation of gold mineralization at the Sukhoi Log deposit was not in equilibrium with igneous rocks at high temperatures.     

Geological setting, mineralogy, geochemistry and genesis of the Middle Archaean Kalyadi copper deposit, western Dharwar craton, southern India

The Kalyadi polymetallic copper deposit occurs within the Middle Archaean (≥3.0 Ga), medium-grade Kalyadi schist belt which consists predominantly of ultramafic-mafic schists interbedded with chemogenic chert, detrital high Al-Mg schists and siliceous schists. This sedimentary exhalative type (SEDEX type) ore-body is the only copper deposit hosted in cherts in the western Dharwar craton. The Kalyadi supracrustal rocks are intruded by tonalite-trondhjemitic gneisses (ca. 3.0 Ga) and granite (ca. 2.6 Ga). The Kalyadi copper deposit is polygenetic in nature. The primary ores represented by disseminations of pyrite ± linneite and chalcopyrite ± magnetite essentially along the bedding lamination of the metachert are referred to as the metamorphosed chert-sulphide rhythmites of a primary stratiform type. The ore is of low-grade and records imprints of at least two events of deformation. Pyrite is characterised by high-Co values (262–4524 ppm) and high–Co/Ni ratios (3.0–19.7). Rare earth element patterns of the primary ores and the host metacherts are identical, characterised by La enrichment, absence of Eu anomalies and flat to depleted HREE patterns with δ ³⁴ S = −0.8‰. The secondary (remobilised) ores are structurally controlled occurring as veins and stringers discordant to the bedding lamination or schistosity. The constituent ores are chalcopyrite-pyrite-pyrrhotite with minor pentlandite. These sulphides with low-Co/Ni ratios (0.87–1.80), have either a strong positive or negative Eu anomaly and show slight HREE enrichment. The δ ³⁴ S value ranges from +2.64 to −4.29‰. It is interpreted that the primary stratiform ores and the cherts were derived from volcanogenic hydrothermal fluids as syngenetic/chemical deposits in a deep sea environment. The secondary epigenetic mineralisation is related to subsequent migmatisation, deformational events and granitic activity. Received: 8 September 1995 / Accepted: 18 November 1996