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1.
Measurements were made of sulphur and oxygen isotope ratios of sulphate in some Slovenian rivers, lakes and tap waters. δ34S ranged from −0.2 to + 13.3‰, δ18O ranged from +4.9 to + 13.6‰, and the sulphate content varied from 0.8 to 41.4 mg/L. Rivers flowing from the Julian Alps contain a very low amount of sulphate that is leached from a thin horizon of soil by rain. As confirmed by their low δ18O values, these sulphates do not enter the rivers directly in rain, but arise from biochemical cycling in the soil. The low δ34S of this sulphate indicates that it originates from the oxidation of sedimentary sulphides. The evolution of sulphates along the river course was investigated for the Sava and Ljubljanica rivers. The variations observed in sulphate from the waters studied result from variations in the contribution of sulphates of different origin. Downstream the Sava River sulphate is depleted in the heavy isotopes of both sulphur and oxygen, with δ-values gradually tending toward the δ-values of groundwater sulphates in the watershed. In contrast, the δ-values of sulphate in the Ljubljanica River are almost constant and similar to those of sulphate in local groundwater. Introduction of water from Italian and Slovenian mines was recorded in the Soča River, where the lowest δ34S value of sulphate sulphur (−0.2‰) was observed. In addition, the influence of sulphate from the oxidation of sedimentary sulphides was recorded in the Sotla River. No evidence was found for introduction of sulphate from factories.  相似文献   

2.
The sulphide deposits of the Iberian Pyrite Belt (IPB) represent an ore province of global importance. Our study presents 113 new sulphur isotope analyses from deposits selected to represent the textural spectrum of ores. Measured 34S values range from −26 to +10‰ mostly for massive and stockwork ores, in agreement with data previously published. In situ laser 34S analyses reveals a close correlation of 34S with texture. Primary diagenetic textures are dominated by relatively low 34S (−8‰ to −2‰), whereas stockwork feeder textures are dominated by higher 34S (∼+3‰ to +5‰). Intermediate textures (mainly coarse textures in stratiform zones) have intermediate 34S, although they are mostly dominated by the high 34S component. Rare barite has a homogeneous 34S around +18‰, which is consistent with direct derivation from Lower Carboniferous seawater sulphate. A dual source of sulphide sulphur in the IPB deposits has been considered. A hydrothermal source, derived from reduction of coeval seawater sulphate in the convective systems, is represented by sulphide in the feeder zones. Here variations in 34S are caused by variations in the extent of the sulphate reduction, which governs the SO4:H2S ratio. The second end-member was derived from the bacterial reduction of coeval seawater sulphate at or near the surface, as reflected in the primary textures. A distinct geographical variation in 34S and texture from SW (more bacteriogenic and primary textures) to NE (more hydrothermal textures and 34S) which reflects a variation in the relative input of each source was likely controlled by local geological environments. Given that the sulphur isotope characteristics of the IPB deposits are unlike most VMS and Kuroko deposits, and noting the dominance of a mixed reduced sedimentary and volcanic environment, we suggest that the IPB could represent an ore style which is intermediate between volcanic and sedimentary hosted massive sulphide types. Received: 8 October 1997 / Accepted: 14 May 1998  相似文献   

3.
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  相似文献   

4.
The strongly deformed Middle Devonian-Lower Carboniferous metasedimentary-volcanic successions of the Trevone Basin (SW England) contain stratiform and Pb-Sb vein deposits that reveal a wide variation in δ34S and δ13C, reflecting mineral deposition during diagenesis, regional metamorphism and basin inversion. Pre-Variscan metasedimentary sulphide (δ34S=−33.7 to −26.7‰) and metabasite sulphide (δ34S=+4.0 to +10.8‰) suggest two accessible source reservoirs for sulphur which were available for Sb-As-(Au) and Pb-Zn-(Ag) mineralisation (δ34S=−3.3 to −15.0‰) during late Variscan semiductile-brittle shear. On the basis of pressure-corrected fluid inclusion temperatures, the calculated composition of fluid sulphur reveals an enrichment in δ34SH2S in the individual vein parageneses and depletion of the fluid sulphur reservoir during evolution of the vein systems. Carbonates in the same veins are partly contemporaneous with Pb-Sb mineralisation and late tensional deformation; their isotopic composition (δ13C=−3.2 and −13.4‰) appears strongly influenced by the host formation. Fluid inclusions in post-tensional quartz show a marked reduction in CO2, suggesting that episodes of CO2 degassing in response to punctuated reductions in pressure during uplift and brittle deformation was an important mechanism for vein carbonation. An origin for the Pb-Sb mineralisation involving local remobilisation of sulphur from the mixed metasedimentary-volcanic succession is probably inseparable from processes connected with Variscan metamorphism and deformation. Although the N Cornish Variscan deformation is part of a spatially large-scale event, the isotopic evidence suggests compartmentalisation of sulphur and carbon isotope features and short distances between sources and sinks. Received: 15 August 1998 / Accepted: 8 October 1999  相似文献   

5.
Luiswishi is a Congo-type Neoproterozoic sediment-hosted stratiform Cu–Co ore deposit of the Central Africa Copperbelt, located northwest of Lubumbashi (DRC). The ores form two main Cu–Co orebodies hosted by the Mines Subgroup, one in the lower part of the Kamoto Formation and the other at the base of the Dolomitic Shales Formation. Sulphides occur essentially as early parallel layers of chalcopyrite and carrolite, and secondarily as late stockwork sulphides cross-cutting the bedding and the early sulphide generation. Both types of stratiform and stockwork chalcopyrite and carrolite were systematically analyzed for sulphur isotopes, along the lithostratigraphic succession of the Mine Series. The quite similar δ34S values of stratiform sulphides and late stockwork sulphides suggest an in situ recrystallization or a slight remobilization of stockwork sulphides without attainment of isotopic equilibrium between different sulphide phases (chalcopyrite and carrolite). The distribution of δ34S values (−14.4‰ to +17.5‰) combined with the lithology indicates a strong stratigraphic control of the sulphur isotope signature, supporting bacterial sulphate reduction during early diagenesis of the host sediments, in a shallow marine to lacustrine environment. Petrological features combined with sulphur isotopic data of sulphides at Luiswishi and previous results on nodules of anhydrite in the Mine Series indicate a dominant seawater/lacustrine origin for sulphates, precluding a possible hydrothermal participation. The high positive δ34S values of sulphides in the lower orebody at Luiswishi, hosted in massive chloritic–dolomitic siltite (known as Grey R.A.T.), fine-grained stratified dolostone (D.Strat.) and silicified-stromatolitic dolomites alternating with chloritic–dolomitic silty beds (R.S.F.), suggest that they were probably deposited during a period of regression in a basin cut off from seawater. The variations of δ34S values (i.e. the decrease of δ34S values from the Kamoto Formation to the overlying Dolomitic Shales and then the slight increase from S.D.2d to S.D.3a and S.D.3b members) are in perfect agreement with the inferred lithological and transgressive–regressive evolution of the ore-hosting sedimentary rocks [Cailteux, J., 1994. Lithostratigraphy of the Neoproterozoic Shaba-type (Zaire) Roan Supergroup and metallogenesis of associated stratiform mineralization. In: Kampunzu A.B., Lubala, R.T. (Eds.), Neoproterozoic Belts of Zambia, Zaire and Namibia. Journal of African Earth Sciences 19, 279–301].  相似文献   

6.
At Sams Creek, a gold-bearing, peralkaline granite porphyry dyke, which has a 7 km strike length and is up to 60 m in thickness, intrudes camptonite lamprophyre dykes and lower greenschist facies metapelites and quartzites of the Late Ordovician Wangapeka formation. The lamprophyre dykes occur as thin (< 3 m) slivers along the contacts of the granite dyke. δ18Omagma values (+5 to +8‰, VSMOW) of the A-type granite suggest derivation from a primitive source, with an insignificant mature crustal contribution. Hydrothermal gold–sulphide mineralisation is confined to the granite and adjacent lamprophyre; metapelite country rocks have only weak hydrothermal alteration. Three stages of hydrothermal alteration have been identified in the granite: Stage I alteration (high fO2) consisting of magnetite–siderite±biotite; Stage II consisting of thin quartz–pyrite veinlets; and Stage III (low fO2) consisting of sulphides, quartz and siderite veins, and pervasive silicification. The lamprophyre is altered to an ankerite–chlorite–sericite assemblage. Stage III sulphide veins are composed of arsenopyrite + pyrite ± galena ± sphalerite ± gold ± chalcopyrite ± pyrrhotite ± rutile ± graphite. Three phases of deformation have affected the area, and the mineralised veins and the granite and lamprophyre dykes have been deformed by two phases of folding, the youngest of which is Early Cretaceous. Locally preserved early-formed fluid inclusions are either carbonic, showing two- or three-phases at room temperature (liquid CO2-CH4 + liquid H2O ± CO2 vapour) or two-phase liquid-rich aqueous inclusions, some of which contain clathrates. Salinities of the aqueous inclusions are in the range of 1.4 to 7.6 wt% NaCl equiv. Final homogenisation temperatures (Th) of the carbonic inclusions indicate minimum trapping temperatures of 320 to 355°C, which are not too different from vein formation temperatures of 340–380°C estimated from quartz–albite stable isotope thermometry. δ18O values of Stage II and III vein quartz range from +12 and +17‰ and have a bimodal distribution (+14.5 and +16‰) with Stage II vein quartz accounting for the lower values. Siderite in Stage III veins have δ18O (+12 to +16‰) and δ13C values (−5‰, relative to VPDB), unlike those from Wangapeka Formation metasediments (δ13Cbulk carbon values of −24 to −19‰) and underlying Arthur Marble marine carbonates (δ18O = +25‰ and δ13C = 0‰). Calculated δ18Owater (+8 to +11‰, at 340°C) and (−5‰) values from vein quartz and siderite are consistent with a magmatic hydrothermal source, but a metamorphic hydrothermal origin cannot be excluded. δ34S values of sulphides range from +5 to +10‰ (relative to CDT) and also have a bimodal distribution (modes at +6 and +9‰, correlated with Stage II and Stage III mineralisation, respectively). The δ34S values of pyrite from the Arthur Marble marine carbonates (range from +3 to +13‰) and Wangapeka Formation (range from −4 to +9.5‰) indicate that they are potential sources of sulphur for sulphides in the Sams Creek veins. Another possible source of the sulphur is the lithospheric mantle which has positive values up to +14‰. Ages of the granite, lamprophyre, alteration/mineralisation, and deformation in the region are not well constrained, which makes it difficult to identify sources of mineralisation with respect to timing. Our mineralogical and stable isotope data does not exclude a metamorphic source, but we consider that the source of the mineralisation can best be explained by a magmatic hydrothermal source. Assuming that the hydrothermal fluids were sourced from crystallisation of the Sams Creek granite or an underlying magma chamber, then the Sams Creek gold deposit appears to be a hybrid between those described as reduced granite Au–Bi deposits and alkaline intrusive-hosted Au–Mo–Cu deposits.  相似文献   

7.
The Transfiguration Cu–Pb–Zn–Ag deposit, enclosed within reduced grey sandstone, is associated with continental red beds of the Lower Silurian Robitaille Formation in the Quebec Appalachians, Canada. The Robitaille Formation rests unconformably on foliated Cambro-Ordovician rocks. The unconformity is locally cut by barite veins. The basal unit of the Robitaille Formation comprises green wacke and pebble conglomerate, which locally contain calcite nodules. The latter have microstructures characteristic of alpha-type calcretes, such as “floating” fabrics, calcite-filled fractures (crystallaria) and circumgranular cracks. Massive, grey sandstone overlies the basal green wacke and pebble conglomerate unit, which is overlain, in turn, by red, fine-grained sandstone. Mineralisation occurred underneath the red sandstone unit, chiefly in the grey sandstone unit, as disseminated and veinlet sulphides. Chalcopyrite, the most abundant Cu sulphide, replaced early pyrite. Calcrete, disseminated carbonate and vein carbonate have stable isotope ratios varying from −7.5‰ to −1.1‰ δ13C and from 14.7‰ to 21.3‰ δ18O. The negative δ13C values indicate the oxidation of organic matter in a continental environment. Sulphur isotope ratios for pyrite, chalcopyrite and galena vary from −19‰ to 25‰ δ34S, as measured on mineral concentrates by a conventional SO2 technique. Laser-assisted microanalyses (by fluorination) of S isotopes in pyrite show an analogous range in δ34S values, from −21‰ to 25‰. Negative and positive δ34S values are compatible with bacterial sulphate reduction (BSR) in systems open and closed with respect to sulphate. We interpret similarly high δ34S values for sulphide concentrates (25.1‰) and for vein barite (26.2‰) to result from rapid and complete thermochemical reduction of pore-water sulphate. Two early to late diagenetic stages of mineralisation best explain the origin of the Transfiguration deposit. The first stage was characterised by the ponding of groundwater over the Taconian unconformity, recorded by calcrete and early pyrite formation via BSR in grey sandstone. Early pyrite contains up to 2 wt.% Pb, which is consistent with Pb fixation by sulphate-reducing bacteria. The second stage (II) is defined by the replacement of early pyrite by chalcopyrite, as well as by sulphide precipitation via either BSR or thermochemical sulphate reduction (TSR) in grey sandstone. This event resulted from the synsedimentary fault-controlled percolation and mixing of (1) an oxidising, sulphate-bearing cupriferous fluid migrating per descensum from the red-bed sequence and (2) a hydrocarbon-bearing fluid migrating per ascensum from the Cambro-Ordovician basement. Mixing between the two fluids led to sulphate reduction, causing Cu sulphide precipitation. The positive correlation between Cu and Fe3+/Fe2+ bulk rock values suggests that Fe acted as a redox agent during sulphate reduction. Stage II diagenetic fluid migration is tentatively attributed to the Late Silurian Salinic extensional event.  相似文献   

8.
The succession of the formation of ore zones and sulfur isotope ratio of sulfides at the Mangazeya Ag deposit have been studied. The deposit is located in the Nyuektame Fault Zone in the eastern limb of the Endybal Anticline. The ore zones are hosted in the Middle Carboniferous to Middle Jurassic terrigenous sequences of the Verkhoyansk Complex intruded by the Endybal subvolcanic stock and felsic and mafic dikes. Three ore stages are distinguished: (I) gold-rare metal, (II) cassiterite-sulfide, and (III) silver-base-metal. Products of these stages are spatially isolated. The δ34S of sulfides ranges from −6.4 to +8.0‰. In the sulfides of the gold-rare metal assemblage, this value varies from −1.8 to +4.7‰; in the sulfides of the cassiterite-sulfide stage, −6.4 to +6.6‰; and in the sulfides of the silver-base-metal assemblage, -5.6 to +8.0‰. A sulfur isotope thermometer indicates the temperature of mineral deposition at 315–415°C for the first stage and 125–280°C for the third stage. Possible causes of variable sulfur isotopic composition in sulfides are discussed. The data on the sulfur isotope ratio is interpreted in terms of involvement of magmatic fluid (δ34S ∼ 0) in the mineralizing process along with low-temperature fluid taking sulfur from host rocks (δ34S ≫ 0). Boiling and mixing of magmatic fluid with heated meteoric water were important at the last stage of the deposit formation.  相似文献   

9.
The Pering deposit is the prime example of Zn–Pb mineralisation hosted by stromatolitic dolostones of the Neoarchean to Paleoproterozoic Transvaal Supergroup. The hydrothermal deposit centers on subvertical breccia pipes that crosscut stromatolitic dolostones of the Reivilo Formation, the lowermost portion of the Campbellrand Subgroup. Four distinct stages of hydrothermal mineralisation are recognised. Early pyritic rock matrix brecciation is followed by collomorphous sphalerite mineralisation with replacive character, which, in turn, is succeeded by coarse grained open-space-infill of sphalerite, galena, sparry dolomite, and quartz. Together, the latter two stages account for ore-grade Zn–Pb mineralisation. The fourth and final paragenetic stage is characterised by open-space-infill by coarse sparry calcite. The present study documents the results of a detailed geochemical study of the Pering deposit, including fluid inclusion microthermometry, fluid chemistry and stable isotope geochemistry of sulphides (δ34S) and carbonate gangue (δ13C and δ18O). Microthermometric fluid inclusion studies carried out on a series of coarsely grained crystalline quartz and sphalerite samples of the latter, open-space-infill stage of the main mineralisation event reveal the presence of three major fluid types: (1) a halite–saturated aqueous fluid H2O–NaCl–CaCl2 (>33 wt% NaCl equivalent) brine, (2) low-salinity meteoric fluid (<7 wt% NaCl) and (3) a carbonic CH4–CO2–HS− fluid that may be derived from organic material present within the host dolostone. Mixing of these fluids have given rise to variable mixtures (H2O–CaCl2–NaCl ±(CH4–CO2–HS−), 2 to 25 wt% NaCl+CaCl2). Heterogeneous trapping of the aqueous and carbonic fluids occurred under conditions of immiscibility. Fluid temperature and pressure conditions during mineralisation are determined to be 200–210°C and 1.1–1.4 kbar, corresponding to a depth of mineralisation of 4.1–5.2 km. Chemical analyses of the brine inclusions show them to be dominated by Na and Cl with lesser amounts of Ca, K and SO4. Fluid ratios of Cl/Br indicate that they originated as halite saturated seawater brines that mixed with lower salinity fluids. Analyses of individual brine inclusions document high concentrations of Zn and Pb (∼1,500 and ∼200 ppm respectively) and identify the brine as responsible for the introduction of base metals. Stable isotope data were acquired for host rock and hydrothermal carbonates (dolomite, calcite) and sulphides (pyrite, sphalerite, galena and chalcopyrite). The ore-forming sulphides show a trend to 34S enrichment from pyrite nodules in the pyritic rock matrix breccia (δ34S = −9.9 to +3.7‰) to paragenetically late chalcopyrite of the main mineralisation event (δ34S = +30.0‰). The observed trend is attributed to Rayleigh fractionation during the complete reduction of sulphate in a restricted reservoir by thermochemical sulphate reduction, and incremental precipitation of the generated sulphide. The initial sulphate reservoir is expected to have had an isotopic signature around 0‰, and may well represent magmatic sulphur, oxidised and leached by the metal-bearing brine. The δ18O values of successive generations of dolomite, from host dolostone to paragenetically late saddle dolomite follow a consistent trend that yields convincing evidence for extensive water rock interaction at variable fluid–rock ratios. Values of δ13C remain virtually unchanged and similar to the host dolostone, thus suggesting insignificant influx of CO2 during the early and main stages of mineralisation. On the other hand, δ13C and δ18O of post-ore calcite define two distinct clusters that may be attributed to changes in the relative abundance in CH4 and CO2 during waning stages of hydrothermal fluid flow.  相似文献   

10.
The present investigation deals with sulphur isotope distribution in Lower Proterozoic iron and sulphide mineralizations in northern Sweden. The contrasting sulphur isotope patterns are indicative of different genesis. Some 267 sulphur isotope analyses of pyrite, pyrrhotite, chalcopyrite, sphalerite, galena and bornite from 23 occurrences have been performed. Some deposits exhibit uniform compositions, although the mean 34S values are clearly different, while other mineralizations have widely fluctuating values.The 34S values in syngenetic, exhalative sedimentary skarn iron ores, quartz-banded iron ores and sulphide mineralizations of the 2.0–2.5 Ga old (Lapponian) Greenstone group show a large spread, supporting the existence of bacteriogenic sulphate reduction processes. The spread of the sulphur isotope values ( 34S = -8 to +25), and the non-equilibrium conditions, point to a biogenic rather than to an inorganic reduction of seawater sulphate.The isotopic composition of the sulphides in the epigenetic Lannavaara iron ores which were formed by a hydrothermal scapolite-tourmalme-related process, indicates a sulphur source similar to that of the Greenstone group. The 34S values of Cu-(Au) sulphide mineralizations in the Malmberget region (e.g. Aitik), which were formed by a similar process and hosted by the volcanics-volcanoclastics of the 1.9 Ga old Porphyry group, are slightly below zero , indicating a magmatic origin. The existence of different sulphur compositions for these mineralization types formed by a similar hydrothermal process, probably reflects the influence of the host rock, the solutions leaching pre-existing sulphides.In southern Norrbotten, epigenetic, Cu-Zn-Pb veintype mineralizations in metavolcanics and metasediments have 34S values close to zero indicating a magmatic origin. The sulphur isotope data of the volcanogenic, massive sulphide ores of the Skellefte district, in particular the ores of the Adak dome, are close to zero .The lead and sulphur isotopic features of the sulphides in northern Sweden show that the ore-forming processes were of a different nature on both sides of the Archean-Proterozoic border, implying differences in the crustal development. Lead isotopes show that lead was mobilized from specific sources on each side of the border. The sulphur of the sulphides in the Greenstone group in NE Sweden and Finland was introduced by sedimentary processes, whereas the sulphur of the sulphide occurrences towards the SW, mainly in the Porphyry group, is dominated by a magmatic sulphur component.  相似文献   

11.
Sulphur isotopic compositions of 29 sulphide samples from the Broken Hill-type Pinnacles Deposit, NSW, are found to cluster at 0%. (mean −0.8‰). The restricted range of the (δ34S) values between −3.5 and + 3.7‰ with a mean of −0.8‰, is interpreted as reflecting partial oxidation of a dominantly magmatic sulphur source. δ34S data for galena samples fall into two groups: (1) isotopically heavier galenas (range −0.7 to 0.0‰; mean −0.4‰) which come mainly from the footwall Zn lode and (2) isotopically lighter galenas (range −3.5 to −0.8‰; mean −2.2‰) which are from the main Pb lode. Sphalerite, pyrrhotite and chalcopyrite have slightly heavier isotopic compositions (range −1.6 to +3.7‰ mean +0.3‰) but exhibit the same stratigraphic differentiation. These data are interpreted as representing fluctuating conditions at the site of ore deposition, in which upwelling hydrothermal fluids were subject to increasing fO2 and decreasing temperature with time.  相似文献   

12.
The Spessart district (SW Germany), located at the southwestern margin of the Permian Kupferschiefer basin in Central Europe, hosts abundant stratabound and structurally controlled base metal mineralization. The mineralization styles identified are (1) stratabound Cu-Pb-Zn-(Ag) ores in Zechstein sedimentary rocks, (2) structurally controlled Cu-As-(Ag) ores in Zechstein sedimentary rocks, (3) crosscutting Co-Ni-(Bi)-As and Cu-Fe-As veins, (4) stratabound metasomatic Fe-Mn carbonate ores in Zechstein dolomite, (5) barren barite veins, and (6) Fe-Mn-As veins in Permian rhyolites. Building on previous work that involved mineralogical, textural, and chemical characterization of the major mineralization types, we have performed a comprehensive sulfur isotope study that applied both conventional and novel laser-ablation multi-collector inductively coupled plasma mass spectrometry techniques. The δ34S values of sulfide minerals from the different ore types are consistently negative and highly variable, in the range between −44.5‰ and −3.9‰, whereas the δ34S values of barite are all positive in the range between 4.7‰ and 18.9‰. Remarkably, stratabound and structurally controlled mineralization in Zechstein sedimentary rocks has the least negative δ34S values, whereas vein-type deposits have consistently more negative δ34S values. The observed pattern of sulfide δ34S values can be best interpreted in terms of fluid mixing at the basement-cover interface. Hydrothermal fluids originating from the crystalline basement migrated upward along subvertical fault zones and were periodically injected into groundwaters that were flowing in the post-Variscan sedimentary cover. These groundwaters had interacted with the Zechstein sedimentary rocks, resulting in fluids characterized by elevated concentrations of reduced sulfur (with negative δ34S values) and alkaline pH. Repeated mixing between both chemically contrasting fluids caused rapid and efficient precipitation of sulfide ore minerals in hydrothermal veins with highly variable but distinctly negative δ34S values.  相似文献   

13.
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.  相似文献   

14.
The origin of sulphates in sulphate-rich efflorescences on quartz sandstones with a clay matrix, exposed in rural areas of the Czech Republic is interpreted, based upon an isotopic study of S and O. Sulphates such as gypsum and/or alums exhibit δ34S ranging from +1.3 to +6.1‰ and δ18O from +5.3 to +8.8‰. The low variability of S and O isotopes indicates a common source of the sulphur and a similar mode of sulphate formation. Atmospheric sulphates with a similar isotopic signature occur in the area, due to the combustion of sulphurous coal in power plants, located a few tens of kilometres from the sampling points. The sulphates crystallize from supersaturated pore waters that represent atmospheric precipitation, rich in sulphates, having percolated through the porous sandstone system. The previously proposed model of efflorescence growth (that it is due to the oxidation of pyrite) can be excluded, due to both the rare occurrence of pyrite and also to its different isotopic signature (δ34S about −22‰). Although gypsum prevails in the central and eastern part of the studied area, the north and north-west of the Bohemian Cretaceous Basin (the most polluted region) exhibits a significant presence of alums (NH4 + or K+−NH4 +-rich). Formation of alums can be explained by the partial dissolution of clay minerals or feldspars present in the sandstone matrix. Release of alumina from these phases is facilitated by the low pH of the precipitation (pH 4–4.5) and also locally by organic acids, traces of which were found in the studied efflorescences by the use of infrared spectroscopy.  相似文献   

15.
A newly discovered, extensive sphalerite-bearing breccia (~7.5 wt.% Zn) is hosted in dolomitised Carboniferous limestones overlying Ordovician–Silurian metasedimentary rocks on the Isle of Man. Although base metal sulphide deposits have been mined historically on the island, they are nearly all quartz vein deposits in the metamorphic basement. This study investigates the origin of the unusual sphalerite breccia and its relationship to basement-hosted deposits, through a combination of petrographic, cathodoluminescence, fluid inclusion, stable isotope and hydrogeologic modelling techniques. Breccia mineralisation comprises four stages, marked by episodes of structural deformation and abrupt changes in fluid temperature and chemistry. In stage I, high-temperature (T h > 300°C), high-salinity (20–45 wt.% equiv. NaCl) fluid of likely basement origin deposited a discontinuous quartz vein. This vein was subsequently dismembered during a major brecciation event. Stages II–IV are dominated by open-space filling sphalerite, quartz and dolomite, respectively. Fluid inclusions in these minerals record temperatures of ~105–180°C and salinities of ~15–20 wt.% equiv. NaCl. The δ34S values of sphalerite (6.5–6.9‰ Vienna-Canyon Diablo troilite) are nearly identical to those of ore sulphides from mines in the Lower Palaeozoic metamorphic rocks. The δ18O values for quartz and dolomite indicate two main fluid sources in the breccia’s hydrothermal system, local Carboniferous-hosted brines (~0.5–6.0‰ Vienna standard mean ocean water) and basement-involved fluids (~5.5–11.5‰). Ore sulphide deposition in the breccia is compatible with the introduction and cooling of a hot, basement-derived fluid that interacted with local sedimentary brines.  相似文献   

16.
Summary A set of 354 sulphur isotope data from the Bleiberg deposit, the type deposit of Alpine low temperature carbonate hosted Pb–Zn deposits (APT deposits), is critically evaluated applying statistical methods. The sulphur isotope patterns vary significantly among the ore horizons. This suggests a long lasting and polyphase mineralisation system. The sulphur isotope composition of barite corresponds to that of Carnian seawater (i.e. 16 34S). The 34S values of the iron sulphides correspond to data from sedimentary iron sulphides. Pb and Zn sulphides are characterized by three normally distributed 34S populations with mean values of –6 to –8, –13 to –18, and –25 to –29. Heavy sulphur (>–10 34S) indicates contribution of sulphide sulphur from epigenetic-hydrothermal fluids, whereas light sulphide sulphur (<–21 34S) was produced by sulphur – reducing bacteria. The intermediate population is explained by mixing of sulphur derived from these two sources. Other sources of local importance, however, can not be excluded. The isotope populations correspond only partly to the paragenetic ore stages. The sulphur isotope patterns in the APT deposits are regionally different. Data from other low-temperature sediment-hosted Pb–Zn deposits support the proposed interpretation. A comparison demonstrates that the sulphur isotope patterns of APT deposits correspond to patterns of the Irish type deposits, but are different to those of Mississippi Valley type deposits.Supplementary material to this paper is available in electronic form at http://dx.doi.org/10.1007/s00710-004-0071-3  相似文献   

17.
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  相似文献   

18.
The sulphur isotope composition of 233 sulphides and 40 sulphates has been investigated and evaluated in combination with 29 earlier published data. The total variation of δ34S values for the sulphides and the sulphates ranges from ?40 up to ?1 ‰ and from +7 up to +20 ‰, respectively. For the mineral species the variations are (with number of samples in brackets): galena (96) ?32 up to ?2 ‰, sphalerite (141) ?30 up to ?4 ‰, marcasite (16) ?27 up to ?1 ‰, pyrite (10) ?26 up to ?13 ‰, molybedenite (3) ?40 up to ?29 ‰, anhydrite and gypsum (8) +15 up to +20 ‰, coelestine (1) +19 ‰, and barite (33) +7 up to +18 ‰. The frequency distribution of the δ34S values corresponds with the complexity of the ore forming processes which resulted in six strata-bound ore mineralizations. The sulphate values clearly show that the sulphate sulphur originates from sea water sulphate. The sulphides are formed by bacteriogeneric processes from seawater sulphate, and their sulphur isotope composition depends on the lithofacies of the sediments as well as on the following diagenetic processes.  相似文献   

19.
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 13CPDB=−6.0 to +4.4‰) and oxygen (δ 18OSMOW=+19.5 to +26.2‰) isotope composition due to the influx of 13C- and 18O-depleted fluvial water. Sulfate sulfur isotope composition (δ 34SCDT=+17.21 to +22.3‰ and δ 18OSMOW=+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.  相似文献   

20.
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.  相似文献   

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