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     

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.     

Sulfur isotopic composition of hydrothermal precipitates from the Lau back-arc: implications for magmatic contributions to seafloor hydrothermal systems

The sulfur isotopic composition of sulfides and barite from hydrothermal deposits at the Valu Fa Ridge back-arc spreading center in the southern Lau Basin has been investigated. Sulfide samples from the White Church area at the northern Valu Fa Ridge have δ³⁴S values averaging +3.8‰ (n= 10) for bulk sphalerite-chalcopyrite mineralization and +4.8‰ for pyrite (n= 10). Barite associated with the massive sulfides exhibits an average of +20.7‰ (n= 10). Massive sulfides from the active Vai Lili hydrothermal field at the central Valu Fa Ridge have much higher δ³⁴S ratios averaging +8.0‰ for bulk sphalerite-chalcopyrite mineralization (n= 5), +9.3‰ for pyrite samples (n= 5), and +8.0‰ and +10.9‰ for a chalcopyrite and a sphalerite separate, respectively. The isotopic composition of barite from the Vai Lili field is similar to that of barite from the White Church area and averages +21.0‰ (n= 8). Sulfide and barite samples from the Hine Hina area at the southern Valu Fa Ridge have δ³⁴S values that are considerably lighter than those observed for samples from the other areas and average −4.9‰ for pyrite (n= 9), −4.0 and −5.7‰ for two samples of sphalerite-chalcopyrite intergrowth, and −3.4‰ for a single chalcopyrite separate. The total spread in the isotopic composition of sulfides from Vai Lili and Hine Hina is more than 20‰ over a distance of less than 30 km. The δ³⁴S values of sulfides at Hine Hina are the lowest values so far reported for volcanic-hosted polymetallic massive sulfides from the modern seafloor. Barite from the Hine Hina field also has unusually light sulfur with δ³⁴S values of +16.1 to +16.7‰ (n= 5). Isotopic compositions of the sulfides at Hine Hina indicate a dramatic decrease in δ³⁴S from ordinary magmatic values and, in the absence of biogenic sulfur and/or boiling, imply a unique ³⁴S-depleted source of probable magmatic origin. Sulfide-barite mineralization in the Hine Hina area is associated with a distinctive alteration assemblage consisting of cristobalite, pyrophyllite, kaolinite, opal-CT, talc, pyrite, native sulfur, and alunite. Similar styles of alteration are typically known from high-sulfidation epithermal systems on land. Alunite-bearing, advanced argillic alteration in the Hine Hina field confirms the role of acidic, volatile-rich fluids, and a δ³⁴S value of +10.4‰ for the sulfur in the alunite is consistent with established kinetic isotope effects which accompany the disproportionation of magmatic SO₂ into H₂S and H₂SO₄. The Hine Hina field occurs near the propagating tip of the Valu Fa back-arc spreading center (i.e., dominated by dike injections and seafloor eruptions) and therefore may have experienced the largest contribution of magmatic volatiles of the three fields. The sulfur isotopic ratios of the hydrothermal precipitates and the presence of a distinctive epithermal-like argillic alteration in the Hine Hina field suggest a direct contribution of magmatic vapor to the hydrothermal system and support the concept that magmatic volatiles may be an important component of some volcanogenic massive sulfide-forming hydrothermal systems. Received: 16 January 1997 / Accepted: 28 October 1997     

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.     

Gold in the Brunswick No. 12 volcanogenic massive sulfide deposit,Bathurst Mining Camp,Canada: Evidence from bulk ore analysis and laser ablation ICP─MS data on sulfide phases

The 329-Mt Brunswick No. 12 volcanogenic massive sulfide deposit (total resource of 163 Mt at 10.4% Zn, 4.2% Pb, 0.34% Cu, and 115 g/t Ag) is hosted within a Middle Ordovician bimodal volcanic and sedimentary sequence. Massive sulfides are for the most part syngenetic, and the bulk of the sulfide ore occurs as a Zn–Pb-rich banded sulfide facies that forms an intimate relationship with a laterally extensive Algoma-type iron formation and defines the Brunswick Horizon. Zone refining of stratiform sulfides is considered to have resulted in the development of a large replacement-style Cu-rich basal sulfide facies, which is generally confined between the banded sulfide facies and an underlying stringer sulfide zone. Complex polyphase deformation and associated lower- to upper-greenschist facies regional metamorphism is responsible for the present geometry of the deposit. Textural modification has resulted in a general increase in grain size through the development of pyrite and arsenopyrite porphyroblasts, which tend to overprint primary mineral assemblages. Despite the heterogeneous ductile deformation, primary features have locally been preserved, such as fine-grained colloform pyrite and base and precious metal zonation within the Main Zone. Base metal and trace element abundances in massive sulfides from the Brunswick No. 12 deposit indicate two distinct geochemical associations. The basal sulfide facies, characterized by a proximal high-temperature hydrothermal signature (Cu–Co–Bi–Se), contains generally low Au contents averaging 0.39 ppm (n = 34). Conversely, Au is enriched in the banded sulfide facies, averaging 1.1 ppm Au (n = 21), and is associated with an exhalative suite of elements (Zn–Pb–As–Sb–Ag–Sn). Finely laminated sulfide lenses hosted by iron formation at the north end of the Main Zone are further enriched in Au, averaging 1.7 ppm (n = 41) and ranging up to 8.2 ppm. Laser ablation inductively coupled plasma-mass spectrometry (ICP-MS) analyses of pyrite (n = 97) from the north end of the Main Zone average 2.6 ppm Au and range from the detection limit (0.015 ppm) to 21 ppm. Overall, these analyses reveal a distinct Au–Sb–As–Ag–Hg–Mn association within pyrite grains. Gold is strongly enriched in large pseudo-primary masses of pyrite that exhibit relict banding and fine-grained cores; smaller euhedral pyrite porphyroblasts, and euhedral rims of metamorphic origin surrounding the pyrite masses, contain much less Au, Sb, Ag, As, and Sn. Arsenopyrite, occurring chiefly as late porphyroblasts, contains less Au, averaging 1.0 ppm and ranging from the detection limit (0.027 ppm) to 6.9 ppm. Depth profiles for single-spot laser ablation ICP-MS analyses of pyrite and arsenopyrite display uniform values of Au and an absence of discrete microscopic inclusions of Au-bearing minerals, which is consistent with chemically bonded Au in the sulfide structure. The pervasive correlation of Au with Sn in the Zn–Pb-rich banded sulfide facies suggests similar hydrothermal behavior during the waxing stages of deposition on the seafloor. Under high temperature (>350oC) and moderate- to low-pH conditions, Au and Sn in hydrothermal fluids would be transported as chlorocomplexes. An abrupt decrease in temperature and aH₂S, accompanied by an increase in fO₂ and pH during mixing with seawater, would lead to the simultaneous destabilization of both Au and Sn chlorocomplexes. The enrichment of Au in fine-grained laminated sulfides on the periphery of the deposit, accompanied by sporadic occurrences of barite and Fe-poor sphalerite, supports lower hydrothermal fluid temperatures analogous to white smoker activity on the flanks of a large volcanogenic massive sulfide system. In lower temperature (<350oC) and mildly acidic hydrothermal fluids, Au would be transported by thiocomplexes, which exhibit multifunctional (retrograde–prograde) solubility and a capacity to mobilize Au to the outer parts of the sulfide mound. The sluggish nature of this low-temperature venting together with larger variations in ambient fO₂ could lead to a sharp enrichment of Au towards the stratigraphic hanging wall of massive sulfide deposits. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Volcanogenic-related origin of sulfide-rich quartz veins: evidence from O and S isotopes at the Géant Dormant gold mine, Abitibi belt, Canada

The Géant Dormant gold mine is a sulfide-rich quartz vein gold deposit hosted by a volcano-sedimentary sequence and an associated felsic endogenous dome and dikes. The auriferous quartz-sulfide veins were preceded by two synvolcanic gold-bearing mineralizing events: early sulfidic seafloor-related and later disseminated pyrite in the felsic dome. This deposit differs from classical Archean auriferous quartz vein deposits by the low carbonate and high sulfide contents of the veins and by their formation prior to ductile penetrative deformation. The δ¹⁸O values of quartz associated with seafloor-related auriferous sulfides average 11.9 ± 0.6‰ (n = 3). The seafloor hydrothermal fluids had a δ¹⁸O value of 3.2‰ calculated at 250 °C. The oxygen isotope composition of quartz and chlorite from veins average 12.5 ± 0.3‰ (n = 20) and 5.9 ± 1.1‰ (n = 4) respectively. Assuming oxygen isotope equilibrium between quartz and chlorite, the veins formed at a temperature of ∼275 °C, which is consistent with the calculated temperature of 269 ± 10 °C from chlorite chemistry. The gold-bearing fluids had a δ¹⁸O value of 4.7‰ calculated at 275 °C. The δ³⁴S values of sulfides from the three gold events range from 0.6 to 2.8‰ (n = 32) and are close to magmatic values. Sulfur isotope geothermometry constrains the sulfide precipitation in the gold-bearing veins at a temperature of ∼350 °C. The similarity of the isotope data, the calculated δ¹⁸O of the mineralizing fluids and the likely seawater fluid source suggest that the three mineralizing events are genetically related to a volcanogenic hydrothermal system. The high value of the auriferous fluids (δ¹⁸O = 4.7‰) is attributed to a significant magmatic fluid contribution to the evolved seawater-dominated convective hydrothermal system. The two-stage filling of veins at increasing temperature from quartz-chlorite (275 °C) to sulfides (350 °C) may reflect the progressive maturation of volcanogenic hydrothermal systems. These results, together with field and geochemical data, suggest that formation of gold-rich volcanogenic systems require specific conditions that comprise a magmatic fluid contribution and gold from arc-related felsic rocks, coeval with the mineralizing events. This study shows that some auriferous quartz-vein orebodies in Archean terranes are formed in volcanogenic rather than mesothermal systems. Received: 12 December 1998 / Accepted: 5 July 1999     

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     

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     

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.     

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.     

Mineralogy of gold in the Elshitsa massive sulphide deposit, Sredna Gora zone, Bulgaria

The Elshitsa volcanic hosted massive sulphide deposit occurs in the central part of the Srena Gora metallogenic zone in Bulgaria. The gold-bearing massive sulphide mineralization is considered to be the product of an island arc volcano-plutonic process and hydrothermal activity that took place during the Late Cretaceous. In addition to the major gold-hosted opaque minerals such as pyrite, chalcopyrite, sphalerite and galena there are minor phases of tennantite, goldfieldite, Se-bearing aikinite, native silver and bornite in the massive sulphide lenses and stringer zones. Most of the sulphide minerals are Se-bearing. All of the six mineral assemblages that were deposited during the pyrite and copper-pyrite stages of mineralization are gold-bearing. The gold tenor as a rule is less than 1 g/t. Native gold and electrum occur as blebs or intergranular particles in the sulphide minerals. Gold in the early massive pyrite is of submicroscopic type (< 0,1 μm) and of colloidal ori-gin. Pyrite deformation and recrystallization in the temperature range 250°–160 °C has led to Au and Ag migration to cracks and grain boundaries of the sulphide minerals. As a result of these process the native gold and electrum grain size increases from submicroscopic (< 0,1 μm) in the early colloform pyrite to microscopic (0,1–100 μm) and macroscopic (> 100 μm) in the late gold-sulphide assemblages. The electrum fineness in 41 individually studied grains varies between 780 and 992‰ with a mean of 895‰. Native silver was found in association with bornite. Cu, Te, Sb and Bi are the most common trace-elements in gold and electrum. The Cu-Zn-Pb association is most important as a Au-Ag-carrier. A model for gold behaviour during sulphide deformation is proposed involving coarsening of gold grain size from the earlier to the later sulphide mineral assemblages. Received: 4 December 1995 / Accepted: 23 September 1996     

H and O isotopic compositions of layered silicates in metasomatites from the Gai Zn-Cu massive sulfide deposit, southern urals

Substantial differences in isotopic compositions of micas and pyrophyllites from metasomatites related to various stages of the process that formed the giant Gai massive sulfide deposit have been established. The illite from the earliest and predominant chlorite-illite-quartz metasomatite is characterized by the least δD values of −(50–85)‰ and δ¹⁸O=7–11‰. The pyrophyllite-quartz metasomatite as well as illite and pyrophyllite schists developed locally in the southern part of the deposit that likely correspond to the site of discharge of late geothermal paleosystem, contain pyrophyllite and illite with much higher values of δD=−(25–45)‰ and δ¹⁸O=4–9‰. Local zones of illite-paragonite schist complete the mineral formation and are characterized by the transitional δD values of −(30–55)‰ and elevated δ¹⁸O of 10–11‰. The most plausible model of isotopic evolution in the hydrothermal system, with an initial temperature of mica formation at 250°C, assumes the mixing of transformed sea water with a magmatic (metamorphic) water at the initial stage when the background metasomatites and massive sulfide orebodies of the northern lode have been formed. Subsequently, after the burial of the northern lode beneath basaltic andesite flows, the repeated sea water invasions took place in the southern discharge site of the system. As a result, the pyrophyllite-quartz metasomatite was formed; the pyrophyllite and illite schists originated in tectonic compression zones. The interaction of this water with silicate rocks was completed by a formation of illite-paragonite schist. In general, the substantial contribution of sea water to the formation of metasomatic halo of the deposit casts no doubt.     

Geochemical characteristics of pyrite in Duolanasayi gold deposit, Xinjiang

The Duolanasayi gold deposit, 60 km NW of Habahe County, Xinjiang Uygur Autonomous Region, is a mid-large-scale gold deposit controlled by brittle-ductile shearing, and superimposed by albitite veins and late-stage magma hydrothermal solutions. There are four types of pyrite, which are contained in the light metamorphosed rocks (limestone, siltstone), altered-mineralized rocks (chlorite-schist, altered albite-granite, mineralized phyllite), quartz veins and carbonatite veinlets. The pyrite is the most common ore mineral. The Au-barren pyrite is present mainly in a simple form and gold-bearing pyrite is present mainly in a composite form. From the top downwards, the pyrite varies in crystal form from {100} and {210} {100} to {210} {100} {111} to {100} {111}. Geochemical studies indicate that the molecular contents of pyrite range from Fe1.057S2 to Fe0.941S2. Gold positively correlates with Mn, Sr, Zn, Te, Pb, Ba and Ag. There are four groups of trace elements: Fe-Cu-Sr-Ag, Au-Te-Co, As-Pb-Zn and Mn-V-Ti-Ba-Ni-Cr in pyrite. The REE characteristics show that the total amount of REE (ΣREE) ranges from 32.35×10 -6 to 132.18×10 -6; LREE/HREE, 4.466-9.142; (La/Yb)N, 3.719-11.133; (Eu/Sm)N, 0.553-1.656; (Sm/Nd)N, 0.602-0.717; La/Yb, 6.26-18.75; δEu, 0.628-2.309; δCe, 0.308-0.816. Sulfur isotopic compositions (δ 34S=-2.46‰--7.02‰) suggest that the sulfur associated with gold mineralization was derived from the upper mantle or lower crust.     

Age and sources of the ore at Tharsis and Rio Tinto, Iberian Pyrite Belt, from Re-Os isotopes

Re-Os isotopes were used to constrain the source of the ore-forming elements of the Tharsis and Rio Tinto mines of the Iberian Pyrite Belt, and the timing of mineralization. The pyrite from both mines has simila]r Os and Re concentrations, ranging between 0.05–0.7 and 0.6–66 ppb, respectively. ¹⁸⁷Re/¹⁸⁸Os ratios range from about 14 to 5161. Pyrite-rich ore samples from the massive ore of Tharsis and two samples of stockwork ore from Rio Tinto yield an isochron with an age of 346 ± 26 Ma, and an initial ¹⁸⁷Os/¹⁸⁸Os ratio of about 0.69. Five samples from Tharsis yield an age of 353 ± 44 Ma with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of about 0.37. A sample of massive sulfide ore from Tharsis and one from Rio Tinto lie well above both isochrons and could represent Re mobilization after mineralization. The pyrite Re-Os ages agree with the paleontological age of 350 Ma of the black shales in which the ores are disseminated. Our data do not permit us to determine whether the Re-Os isochron yields the original age of ore deposition or the age of the Hercynian metamorphism that affected the ores. However, the reasonable Re-Os age reported here indicates that the complex history of the ores that occurred after the severe metamorphic event that affected the Iberian Pyrite Belt massive sulfide deposits did not fundamentally disturb the Re-Os geochronologic system. The highly radiogenic initial Os isotopic ratio agrees with previous Pb isotopic studies. If the initial ratio is recording the initial and not the metamorphic conditions, then the data indicate that the source of the metals was largely crustal. The continental margin sediments that underlie the deposits (phyllite-quartzite group) or the volcanic rocks (volcanogenic-sedimentary complex) in which the ores occur are plausible sources for the ore-forming metals and should constrain the models for the genesis of these deposits. Received: 15 March 1999 / Accepted: 26 July 1999     

Geochemistry and genesis of the Lengenbach Pb-Zn-As-Tl-Ba-mineralisation,Binn Valley,Switzerland

 The Lengenbach Pb-Zn-As-Tl-Ba mineralisation is located in Triassic dolostones of the Penninic zone in the Swiss Alps where Alpine metamorphism reached upper greenschist to lower amphibolite grade. Geochemical data are used to constrain the origin of this unique occurrence. Two metamorphic redox environments are present: the As(III)-rich zone is controlled by barite-pyrite while the reduced zone contains graphite or pyrrhotite-pyrite and formally zerovalent As. The As(III)-rich zone is characterised by a mineral assemblage consistent with fO₂ in the stability field of barite+pyrite. An As-(Pb, Tl)-rich sulphide melt coexisted with a hydrothermal fluid at >kk300 °C in this zone. Mineralised dolostones are anomalous in As, Pb, Ag, Tl, Hg, Zn, Ba, Cd, Fe, Cu, Mo, U, V, B, Ga, Cr and possibly Sn and Au (in order of decreasing enrichment). As, Pb and Zn are present in the 0.1 to 1% range, Tl and Ag reach several hundred ppm. Uraninite is concentrated in silicate-rich bands and yields a late Alpine U-Pb age of 18.5±0.5 Ma. Pb- and S isotopic variations are interpreted by metamorphic overprinting and re-equilibration within an isochemically metamorphosed mineralisation. Hydrothermal sulphides are more strongly affected by uranogenic Pb than massive Pb-As-sulphides representing a former sulphide melt. The least overprinted mineralisation is characterised by ²⁰⁶Pb/²⁰⁴Pb U003U=18.44−18.56, ²⁰⁷Pb/²⁰⁴Pb=15.60−15.75, ²⁰⁸Pb/²⁰⁴Pb =38.44−38.84 and δ³⁴S (sulphide)=−25±2‰. S isotopic variations are largely a result of sulphide-sulphate re-equilibration yielding temperatures of 450± 30 °C. ⁸⁷Sr/⁸⁶Sr ratios of mineralised samples are lower than or equal to host dolostones, precluding major infiltration of basement-derived fluids during Alpine metamorphism. The Sr source (⁸⁷Sr/⁸⁶Sr close to 0.708) probably was seawater with a radiogenic, detrital mineral component. The genesis of the unique Lengenbach mineralisation is interpreted as the result of isochemical metamorphic overprinting of a carbonate hosted stratiform sulphide mineralisation. Well-crystallised sulphide minerals in fissures and druses formed during retrograde cooling of a sulphide melt in equilibrium with a hydrothermal fluid. The primary mineralisation was probably formed at or close below the sea floor and fed by sulphide-poor hydrothermal fluids. Sulphide was largely derived from seawater by open system bacterial sulphate reduction. U, V and Mo may be seawater-derived. Received: 1 February 1995/Accepted: 10 January 1996     

Sulfur isotopic composition of the Bainiuchang super-large Ag polymetallic deposit, Yunnan Province, China： Implications for the source of sulfur in ore-forming fluids

The Bainiuchang deposit in Yunnan Province, China, is located geographically between the Gejiu ore field and the Dulong ore field. In addition to >7000 t Ag reserves, the deposit possesses large-scale Pb, Zn, Sn reserves and a mass of dispersed elements (i.e., In, Cd, Ge, Ga, etc.). Based on systematic studies of sulfur isotopic composition, the authors conclude: The Bainiuchang deposit experienced two epochs of metallogenesis, i.e., the Middle-Cambrian sea-floor exhalative sedimentary metallogenic epoch and the Yanshanian magmatic hydrothermal superimposition metallogenic epoch. In the two metallogenic epochs, the δ³⁴S values of sulfides were all near 0, showing a tendency of being enriched slightly in heavy sulfur. The δ³⁴S values of sulfides in the early metallogenic epoch are within the range of 2‰–5‰ with a peak value range of 2‰–3‰ and an average of 3.0‰, and those of sulfides in the late metallogenic epoch are within the range of 2‰–6‰ with a peak value of 3‰–4‰ and an average of 3.9‰. For the single metallogenic epoch, sulfur in the ore-forming fluids in the early epoch already reached isotopic equilibrium and was derived mainly from underneath the magma chamber or basement metamorphic igneous rocks. Sulfur in the sulfides in the late epoch was derived mainly from magmatic hydrothermal fluids formed in the process of remelting of the basement metamorphic igneous rocks.     

Geology, geochemistry and sulfur isotope composition of the Late Proterozoic Jingtieshan (Superior-type) hematite-jasper-barite iron ore deposits associated with stratabound Cu mineralization in the Gansu Province, China

The Jingtieshan deposit occurs in a Precambrian tectonic-stratigraphic terrane within the Northern Qilian Caledonian Orogen, and is generally considered as a Superior-type iron formation. The deposit is characterized by Fe-Si-Ba and Cu mineralization and consists of two types of orebodies, an upper jasper-barite-iron deposit and a lower copper sulfide deposit. The iron orebodies occur as independent stratigraphic layers concordant within a thick argillaceous succession, and exhibit fine-grained textures and well-developed sedimentary layering. The ores are predominantly composed of specularite and jasper with lesser amounts of magnetite, hematite, siderite, and barite. The presence of barite, hematite and jasper as major components shows that the iron ores were precipitated in a relatively oxidized ocean floor environment. The Cu orebody directly underlies the iron ore and is hosted by chlorite-sericite-quartz phyllite. The Cu mineralization is composed of pyrite and chalcopyrite and is characterized by stockwork. The disseminated and stockwork Cu mineralization is metamorphosed and concordant with respect to foliation, indicating pre-fabric development, i.e. pre-metamorphism, and was probably originally formed by reduced fluids reacting at the base of and within the oxide iron formation. Geochemical data show that the jasper-barite-iron ores, which resemble Superior-type iron formations, have a high input of hydrothermal-hydrogeneous elements (SiO₂, av.=56%; Fe₂O_3t, av.=30%; Mn, av.=0.45%; BaO, av.=16.7%) with minimal terrigeneous input (<15% combined Al₂O₃, TiO₂, K₂O, MgO, etc.). The δ³⁴S of exhalative barite varies from 28 to 34‰, which is very heavy with respect to other Late Proterozoic sulfate-bearing deposits, except those of circa 600 Ma in which the sulfides range from 8 to 20‰. The sulfur isotope data indicate that the barite was formed by the mixing of a Ba-rich hydrothermal fluid with sulfate-rich ambient seawater and that the sulfides ores were most probably derived from the reduction of seawater sulfate during subsurface reaction with ferrous iron-bearing minerals. These data are consistent with the jasper-barite-iron deposit forming by hydrothermal exhalative and chemical sedimentary processes on the floor of an ocean basin, and with the Cu mineralization forming by hydrothermal filling and replacement in base of and within the iron formation. Received: 19 March 1997 / Accepted: 14 May 1998     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

Marble-hosted sulfide ores in the Angouran Zn-(Pb–Ag) deposit, NW Iran: interaction of sedimentary brines with a metamorphic core complex

The Angouran Zn-(Pb–Ag) deposit, Zanjan Province, NW Iran, is located within the central Sanandaj-Sirjan Zone of the Zagros orogenic belt. The deposit has proven and estimated resources of 4.7 Mt of sulfide ore at 27.7% Zn, 2.4% Pb, and 110 g/t Ag, and 14.6 Mt of oxidized carbonate ores at 22% Zn and 4.6% Pb. It is hosted by a metamorphic core complex that is unconformably overlain by a Neogene volcanic and evaporite-bearing marine to continental sedimentary sequence. The sulfide orebody, precursor to the significant nonsulfide ores, is located at the crest of an open anticline at the contact between Neoproterozoic to Cambrian footwall micaschists and hanging wall marbles. ⁴⁰Ar–³⁹Ar data on muscovite from mineralized and unaltered footwall micaschists suggest a rapid Mid-Miocene exhumation of the metamorphic basement (∼20 Ma) and yield an upper age constraint for mineralization. The fine-grained sulfide ore is massive, replacive, often brecciated, clearly postmetamorphic and dominated by Fe-poor sphalerite, with minor galena, pyrite, anhydrite, quartz, muscovite, dolomite, and rare calcite. Sphalerite contains Na–Ca–Cl brine inclusions (23–25 mass% total dissolved solids) with homogenization temperatures of 180–70°C. Fluid inclusion chemistry (Na–K–Li–Ca–Mg–Cl–Br), ore geochemistry, S, and Pb isotope data suggest that the Angouran sulfide ore formed by the interaction of modified, strongly evaporated Miocene seawater and the lithotypes of an exhumed metamorphic core complex. Minor contributions of metals from Miocene igneous rocks cannot be excluded. Mineralization occurred in a collisional intra-arc setting with high heat flow, probably during the transition from an extensional to a compressional regime. The Angouran deposit may represent a new type of low-temperature carbonate-hosted Zn–Pb ore that is distinct from Mississippi Valley type and sedimentary-exhalative deposits.Editorial handling: B. Lehmann     

Geology,mineralogy, and sulfur isotope geochemistry of the Sargaz Cu–Zn volcanogenic massive sulfide deposit,Sanandaj–Sirjan Zone,Iran

The Sargaz Cu–Zn massive sulfide deposit is situated in the southeastern part of Kerman Province, in the southern Sanandaj–Sirjan Zone of Iran. The stratigraphic footwall of the Sargaz deposit is Upper Triassic to Lower Jurassic (?) pillowed basalt, whereas the stratigraphic hanging wall is andesite. Mafic volcanic rocks are overlain by andesitic volcaniclastics and volcanic breccias and locally by heterogeneous debris flows. Rhyodacitic flows and volcaniclastics overlie the sequence of basaltic and andesitic rocks. Based on the bimodal nature of volcanism, the regional geologic setting and petrochemistry of the volcanic rocks, we suggest massive sulfide mineralization in the Sargaz formed in a nascent ensialic back-arc basin. The current reserves (after ancient mining) of the Sargaz deposit are 3 Mt at 1.34% Cu, 0.38% Zn, 0.08%Pb, 0.24 g/t Au, and 7 g/t Ag. The structurally dismembered massive sulfide lens is zoned from a pyrite-rich base, to a pyrite?±?chalcopyrite-rich central part, and a sphalerite–chalcopyrite-rich upper part, with a sphalerite-rich zone lateral to the upper part. The main sulfide mineral is pyrite, with lesser chalcopyrite and sphalerite. The feeder zone, comprised of a vein stockwork consists of quartz–sulfide–sericite pesudobreccia and, in the deepest part, chlorite–quartz–pyrite pesudobreccia. Footwall hydrothermal alteration extends at least 70–80 m below the massive sulfide lens and more than a hundred meters along strike from the massive sulfide lens. Jasper and Fe–Mn bearing chert horizons lateral to the sulfide deposit represent low-temperature hydrothermal precipitates of the evolving hydrothermal system. Based on mineral textures and paragenetic relationships, the growth history of the Sargaz deposit is complex and includes: (1) early precipitation of sulfides (protore) on the seafloor as precipitation of fine-grained anhedral pyrite, sphalerite, quartz, and barite; (2) anhydrite precipitation in open spaces and mineral interstices within the sulfide mound followed by its subsequent dissolution, formation of breccia textures, and mound clasts and precipitation of coarse-grained pyrite, sphalerite, tetrahedrite–tennantite, galena and barite; (3) replacement of pre-existing sulfides by chalcopyrite precipitated at higher temperatures (zone refining); (4) continued “refining” led to the dissolution of stage 3 chalcopyrite and formation of a base-metal-depleted pyrite body in the lowermost part of the massive sulfide lens; (5) carbonate veins were emplaced into the sulfide lens, replacing stage 2 barite. The δ³⁴S composition of the sulfides ranges from +2.8‰ to +8.5‰ (average, +5.6‰) with a general increase of δ³⁴S ratios with depth within the massive sulfide lens and underlying stockwork zone. The heavier values indicate that some of the sulfur was derived from seawater sulfate that was ultimately thermochemically reduced in deep hydrothermal reaction zones.