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1.
Massive Zn‐Pb‐Ag sulfide mineralization appears conformable with felsic volcanism, developed in an Upper Jurassic volcanic arc to the Southwest (SW) of the Serbo‐Macedonian continent in Northern Greece. The host volcanic sequence of the mineralization comprises mylonitized rhyolitic to rhyodacitic lavas, pyroclastics, quartz‐feldspar porphyries, and cherty tuffs. A “white mica—quartz—pyrite” mineral assemblage characterizes the volcanic rocks in the footwall and hanging‐wall of massive sulfide ore layers, formed as a result of greenschist‐grade regional metamorphism on “clay‐quartz‐pyrite” hydrothermal alteration haloes. Massive ore lenses are usually underlain by deformed Cu‐pyrite and quartz‐pyrite stockworks. Most of the sulfide ore bodies have proximal‐type features. Ductile deformation and regional metamorphism have transformed many of the stockwork structures. The mineralization is characterized by high Zn, Pb, and Ag contents, while Cu and critical metals are low. Primary depositional textures, for example, layering, clastic pyrite, colloform, and atoll textures were identified. The overall textural features of the mineralization indicate it has undergone mechanical deformation. The most prominent features of the effects of metamorphism, folding and shearing, are modification of the ore body morphology toward flattened and boudinage structures and transformation of the ore textures toward the dominance of planar fabrics. Sulfur isotope analyses of sulfides along with textural observations are consistent with a dual source of sulfide sulfur. Sulfur isotope values for sphalerite, non‐colloform pyrite, galena, and chalcopyrite fall in a limited range from ?1.6 to +4.8‰ (mean δ34S + 2‰), indicating a hydrothermal source derived from the reduction of coeval seawater sulfate in the convective system. Pyrites with colloform and atoll textures are characterized by a 34S depletion, indicating a bacterial reduction of coeval seawater sulfate. The morphology of ore beds, the mineralogy, sulfide textures, and ore chemistry along with the petrology and tectonic setting of the host rocks can be attributed to typical of a bimodal‐felsic metallogenesis. Although similar in many respects to classic Kuroko‐type volcanogenic massive sulfide mineralization, it has some atypical features, like the absence of barite ore, which is possibly a result of significant temporal depletion in sulfate due to bacterial reduction, a conclusion supported by the widespread occurrence of colloidal and atoll textures of pyrite.  相似文献   

2.
The Chahmir zinc–lead deposit (1.5 Mt @ 6 % Zn + 2 % Pb) in Central Iran is one among several sedimentary-exhalative Zn–Pb deposits in the Early Cambrian Zarigan–Chahmir basin (e.g., Koushk, Darreh-Dehu, and Zarigan). The deposit is hosted by carbonaceous, fine-grained black siltstones, and shales interlayered with volcaniclastic sandstone beds. It corresponds to the upper part of the Early Cambrian volcano-sedimentary sequence (ECVSS), which was deposited on the Posht-e-Badam Block during back-arc rifting of the continental margin of Central Iran. Based on crosscutting relationships, mineralogy, and texture of sulfide mineralization, four different facies can be distinguished: stockwork (feeder zone), massive ore, bedded ore, and distal facies (exhalites with barite). Silicification, carbonatization, sericitization, and chloritization are the main wall-rock alteration styles; alteration intensity increases toward the proximal feeder zone. Fluid inclusion microthermometry was carried out on quartz associated with sulfides of the massive ore. Homogenization temperatures are in the range of 170–226 °C, and salinity is around 9 wt% NaCl eq. The size distribution of pyrite framboids of the bedded ore facies suggests anoxic to locally suboxic event for the host basin. δ34S(V-CDT) values of pyrite, sphalerite, and galena range from +10.9 to +29.8?‰. The highest δ34S values correspond to the bedded ore (+28.6 to +29.8?‰), and the lowest to the massive ore (+10.9 to +14.7?‰) and the feeder zone (+11.3 and +12.1?‰). The overall range of δ34S is consistent with a sedimentary environment where sulfide sulfur was derived from two sources. One of them was corresponding to early ore-stage sulfides in bedded ore and distal facies, consistent with bacterial reduction from coeval seawater sulfate in a closed or semiclosed basin. However, the δ34S values of late ore-stage sulfides, observed mainly in massive ore, interpreted as a hydrothermal sulfur component, leached from the lower part of the ECVSS. Sulfur isotopes, along with the sedimentological, textural, mineralogical, fluid inclusion, and geochemical characteristics of the Chahmir deposit are in agreement with a vent-proximal (Selwyn type) SEDEX ore deposit model.  相似文献   

3.
The Huangshaping Pb–Zn–W–Mo polymetallic deposit, located in southern Hunan Province, China, is one of the largest deposits in the region and is unique for its metals combination of Pb–Zn–W–Mo and the occurrence of significant reserves of all these metals. The deposit contains disseminated scheelite and molybdenite within a skarn zone located between Jurassic granitoids and Carboniferous sedimentary carbonate, and sulfide ores located within distal carbonate-hosted stratiform orebodies. The metals and fluids that formed the W–Mo mineralization were derived from granitoids, as indicated by their close spatial and temporal relationships. However, the source of the Pb–Zn mineralization in this deposit remains controversial.Here, we present new sulfur, lead, and strontium isotope data of sulfide minerals (pyrrhotite, sphalerite, galena, and pyrite) from the Pb–Zn mineralization within the deposit, and these data are compared with those of granitoids and sedimentary carbonate in the Huangshaping deposit, thereby providing insights into the genesis of the Pb–Zn mineralization. These data indicate that the sulfide ores from deep levels in the Huangshaping deposit have lower and more consistent δ34S values (− 96 m level: + 4.4‰ to + 6.6‰, n = 13) than sulfides within the shallow part of the deposit (20 m level: + 8.3‰ to + 16.3‰, n = 19). The δ34S values of deep sulfides are compositionally similar to those of magmatic sulfur within southern Hunan Province, whereas the shallower sulfides most likely contain reduced sulfur derived from evaporite sediments. The sulfide ores in the Huangshaping deposit have initial 87Sr/86Sr ratios (0.707662–0.709846) that lie between the values of granitoids (0.709654–0.718271) and sedimentary carbonate (0.707484–0.708034) in the Huangshaping deposit, but the ratios decreased with time, indicating that the ore-forming fluids were a combination of magmatic and formation-derived fluids, with the influence of the latter increasing over time. The lead isotopic compositions of sulfide ores do not correlate with sulfide type and define a linear trend in a 207Pb/204Pb vs. 206Pb/204Pb diagram that is distinct from the composition of the disseminated pyrite within sedimentary carbonates and granitoids in the Huangshaping deposit, but is similar to the lead isotopic composition of sulfides within coeval skarn Pb–Zn deposits in southern Hunan Province. In addition, the sulfide ores have old signatures with relative high 207Pb/206Pb ratios, suggesting that the underlying Paleoproterozoic basement within southern Hunan Province may be the source of metals within the Huangshaping deposit.The isotope geochemistry of sulfide ores in the Huangshaping deposit shows a remarkable mixed source of sulfur and ore-forming fluids, and the metals were derived from the basement. These features are not found in representative skarn-type Pb–Zn mineralization located elsewhere. The ore-forming elements (S, Pb, and Zn) from the granitoids made an insignificant contribution to sulfide precipitation in this deposit. However, the emplacement of granitoids did provide large amounts of heat and fluids to the hydrothermal system in this area and extracted metals from the basement rocks, indicating that the Jurassic magmatism associated with the Huangshaping deposit was crucial to the Pb–Zn mineralization.  相似文献   

4.

The stable enrichment of pyrite from magnesite ores in δ34S isotope (from 5.4 to 6.9‰) compared with pyrite from the host (sedimentary and igneous) rocks was established in the classical Satka sparry magnesite ore field. Concretionary segregations of fine-grained pyrite in dolomite are depleted in the heavy sulfur isotope (δ34S, from–9.1 to–5.8‰). Pyrite from dolerite is characterized by δ34S values (–1.1 and 1.7‰) close to the meteorite sulfur. The δ34S values in barite from the underlying dolomite horizon vary in the range of 32.3–41.4‰. The high degree of homogeneity of the sulfur isotope composition in pyrite from magnesite is a result of thermochemical sulfate reduction during the syngenetic crystallization of pyrite and magnesite from epigenetic brines, formed during dissolution of evaporite sulfate minerals at the stage of early catagenesis of the Riphean deposits.

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5.
The Turhal antimony sulfide ore deposits are hosted by a Permian-Jurassic sequence which consists of black phyllites at the base followed by interbedded phyllites and calcareous quartzites with metabasite interlayers and then by brown-gray phyllites with marble blocks. Four different styles and three distinct episodes of mineralization were distinguished according to deposition features of the ores and kinkbands in the stibnite crystals. Stibnite from stratiform, disseminated and vein occurrences as well as pyrite from black phyllites showed the following sulfur isotope composition (34S): +2.8 and +3.0 for stratiform stibnite (n = 2), +3.6 and +5.5 for disseminated stibnite (n = 2), +2.5 to +7.8 for vein stibnite (n = 11) and -6.1 to +0.1 for pyrite (n = 3). The 34S compositions of stibnite are interpreted as suggesting an ultimately single source for sulfur in the various styles of mineralization, i.e. synsedimentary volcanic exhalations for the stratiform and disseminated together with ores and hydrothermal mobilisation of these as well as leaching of volcanic rocks to form the vein ores. Deep basinal fluids probably under normal geothermal gradient conditions caused the leaching of the primary sulfides as suggested by the oxygen isotope composition of vein quartz associated with the ores. By contrast sulfur in pyrite is essentially a derivation of seawater sulfate through bacterial and/or chemical reduction.  相似文献   

6.
The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ34S range between ?29.8 and + 10.2‰ and Δ33S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ34SCRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ34S and Δ33S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ34S and Δ33S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ34S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO2 contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.  相似文献   

7.
Volcanic‐hosted massive sulfide (VHMS) deposits of the eastern Lachlan Fold Belt of New South Wales represent a VHMS district of major importance. Despite the metallogenic importance of this terrane, few data have been published for sulfur isotope distribution in the deposits, with the exception of previously published studies on Captains Flat and Woodlawn (Captains Flat‐Goulburn Trough) and Sunny Corner (Hill End Trough). Here is presented 105 new sulfur isotope analyses and collation of a further 92 analyses from unpublished sources on an additional 12 of the VHMS systems in the Hill End Trough. Measured δ34S values range from ‐7.4% to 38.3%, mainly for massive and stockwork mineralisation. Sulfur isotope signatures for polymetallic sulfide mineralisation from the Lewis Ponds, Mt Bulga, Belara and Accost deposits (group 1) are all very similar and vary from ‐1.7% to 5.9%. Ore‐forming fluids for these deposits were likely to have been reducing, with sulfur derived largely from a magmatic source, either as a direct magmatic contribution accompanying felsic volcanism or indirectly through dissolution and recycling of rock sulfide in host volcanic sequences. Sulfur isotope signatures for sulfide mineralisation from the Calula, Commonwealth, Cordillera and Kempfield deposits, Peelwood mine and Sunny Corner (group 2) are similar and have average δ34S values ranging from 5.4% to 8.1%. These deposits appear to have formed from ore fluids that were more oxidising than group 1 deposits, representing a mixed contribution of sulfur derived from partial reduction of seawater sulfate, in addition to sulfur from other sources. The δ34S values for massive sulfides from the John Fardy deposit are the highest in the present study and have a range of 11.9–14.5%, suggesting a greater component of sulfur of seawater origin compared to other VHMS deposits in the Hill End Trough. For barite the sulfur isotope composition for samples from the Commonwealth, Stringers and Kempfield deposits ranges from 12.6% to 38.3%. More than 75% of barite samples have a sulfur isotope composition between 23.4 and 30.6%, close to the previously published estimates of the composition of seawater sulfate during Late Silurian to earliest Devonian times, providing supporting evidence that these deposits formed concurrently with the Late Silurian volcanic event. Sulfur isotope distribution appears to be independent of the host rock unit, although there appears to be a relation linking the sulfur isotope composition of different deposits to defined centres of felsic volcanism. The Mt Bulga, Lewis Ponds and Accost systems are close to coherent felsic volcanic rocks and/or intrusions and have sulfur isotope signatures with a stronger magmatic affinity than group 2 deposits. By contrast, group 2 deposits (including John Fardy) are characterised by 34S‐enrichment and a lesser magmatic signature, are generally confined to clastic units and reworked volcanogenic sediments with lesser coherent volcanics in the local stratigraphy, and are interpreted to have formed distal from the magmatic source. An exception is the Belara deposit, which is hosted by reworked felsic volcanic rocks and has a more pronounced magmatic sulfur isotope signature.  相似文献   

8.
The S-isotope composition (δ34SCDT) of 213 samples of sulfides, sulfates and native sulfur from the pyrite mineralizations of southern Tuscany and associated country rocks were determined. The sulfur isotopic composition of pyrite is quite homogeneous and similar for all studied ore bodies, with an average δ34S value near +9,5‰. Pyrite disseminated within the Filladi di Boccheggiano formation, and thought to be authigenic, shows a much larger range of δ34S values (-13.1 to +14.5‰). The isotopic compositions of other sulfides associated with pyrite in the deposits show that isotopic equilibrium among sulfides was approached on a regional scale, but seldom fully attained. Isotopic data suggest that sedimentary marine sulfate was the ultimate source of sulfur in ores. Sulfates (mostly anhydrite) from the sulfate-carbonate lenses associated with both the Filladi di Boccheggiano and the Calcare Cavernoso formations also have similar and homogeneous compositions (average δ34S=+15–16‰). Coexisting sulfates and sulfides are not in isotopic equilibrium. In the light of the isotopic data, among the many proposed genetic models for the largest stratabound pyrite bodies the two following alternatives appear the most likely: 1) in agreement with recently suggested hypotheses, the ore bodies are older than the emplacement of the Mio-Pliocenic granitoids in the area, and are probably hydrothermal-sedimentary in origin, coeval with associated country rocks; 2) the ore bodies were formed as a consequence of bacterial reduction of anhydrite in low-temperature convection systems related to the early stages of the Mio-Pliocenic thermal anomaly. In both cases, the emplacement of the Mio-Pliocenic granitoids caused metamorphism and remobilization of the pre-existing ores, producing smaller discordant mineralized bodies.  相似文献   

9.
The Chehugou Mo–Cu deposit, located 56 km west of Chifeng, NE China, is hosted by Triassic granite porphyry. Molybdenite–chalcopyrite mineralization of the deposit mainly occurs as veinlets in stockwork ore and dissemination in breccia ore, and two ore‐bearing quartz veins crop out to the south of the granite porphyry stock. Based on crosscutting relationships and mineral paragenesis, three hydrothermal stages are identified: (i) quartz–pyrite–molybdenite ± chalcopyrite stage; (ii) pyrite–quartz ± sphalerite stage; and (iii) quartz–calcite ± pyrite ± fluorite stage. Three types of fluid inclusions in the stockwork and breccia ore are recognized: LV, two‐phase aqueous inclusions (liquid‐rich); LVS, three‐phase liquid, vapor, and salt daughter crystal inclusions; and VL, two‐phase aqueous inclusions (gas‐rich). LV and LVS fluid inclusions are recognized in vein ore. Microthermometric investigation of the three types of fluid inclusions in hydrothermal quartz from the stockwork, breccia, and vein ores shows salinities from 1.57 to 66.75 wt% NaCl equivalents, with homogenization temperatures varying from 114°C to 550°C. The temperature changed from 282–550°C, 220–318°C to 114–243°C from the first stage to the third stage. The homogenization temperatures and salinity of the LV, LVS and VL inclusions are 114–442°C and 1.57–14.25 wt% NaCl equivalent, 301–550°C and 31.01–66.75 wt% NaCl equivalent, 286–420°C and 4.65–11.1 wt% NaCl equivalent, respectively. The VL inclusions coexist with the LV and LVS, which homogenize at the similar temperature. The above evidence shows that fluid‐boiling occurred in the ore‐forming stage. δ34S values of sulfide from three type ores change from ?0.61‰ to 0.86‰. These δ34S values of sulfide are similar to δ34S values of typical magmatic sulfide sulfur (c. 0‰), suggesting that ore‐forming materials are magmatic in origin.  相似文献   

10.
This study examines the sulfur isotope record of seawater sulfate proxies using δ34S and Δ33S to place constraints on the average global fractionation (Δ34Spy) associated with pyrite formation and burial and the exponent λ that relates variations of the 34S/32S to variations of the 33S/32S. The results presented here use an analysis of the sulfur isotope record from seawater sulfate proxies and sedimentary sulfide to extract this quantity as the arithmetic difference between δ34S of seawater sulfate and contemporaneous sulfide. It also uses an independent method that draws on inferences about the Δ33S evolution of seawater sulfate to evaluate this further. These two methods yield similar results suggesting that Δ34Spy and λ changed over the course of the Phanerozoic from slightly lower values of Δ34Spy (lower values of λ) in the early Phanerozoic (Cambrian-Permian) to higher values of Δ34Spy (higher values of λ) starting in the Triassic. This change of Δ34Spy and the exponent λ is interpreted to reflect a change in the proportion of sulfide that was reoxidized and processed by bacterial disproportionation on a global scale. The revised record of Δ34Spy also yields model pyrite burial curves making them more closely resemble model evolution curves for other element systems and global sea level curves. It is suggested that possible links to sea level may occur via changes in the area of submerged continental shelves which would provide additional loci for pyrite burial.The slightly different constraints used by the two approaches to calculate this fractionation may allow for additional information to be obtained about the sulfur cycle with future studies. For instance, the correspondence of these results suggests that the inferred variation of 34S/32S of pyrite is real, and that there is no significant missing sink of fractionated sulfur at the resolution of the present study (such as might be associated with organic sulfur). Burial of organic sulfur may, however, have been important at some times in the Phanerozoic and shorter timescale deviations between results provided by these methods may be observed with higher resolution sampling. If observed, this would suggest either that the record for pyrite (or less likely sulfate) is biased, or that another sink (possibly as organic sulfur) was important during these times in the Phanerozoic.  相似文献   

11.
Pyrite from altered basalts from Nàmafjall and Krafla high-temperature fields and deep zones at Reykir, Leira and other low-temperature fields, and aqueous sulfides from Nàmafjall, have δ34S values of 0 to 2.6%. These values are close to those for postglacial basaltic lavas from the Reykjanes Peninsula. The major source of sulfur in these meteoric hydrothermal systems is the upper-mantle or basalt. At the low-temperature fields, however, the δ34S values of sulfide decrease with decreasing depth, suggesting the presence of a light sulfur source in the shallower aquifers.In contrast, in the Reykjanes and Svartsengi geothermal fields, where seawater contributes to the hydrothermal systems, sulfide sulfur is distinctly enriched in 34S at all depths except for one Reykjanes pyrite from 84 m depth. The enrichment is about 8%. at the deepest core (1734 m) of Reykjanes and decreases with decreasing depth. These enrichments are most likely due to seawater sulfate being involved in the hydrothermal systems. However, in the Reykjanes fluid, dissolved heavy sulfates are not in isotopic equilibrium with sulfide. Disequilibrium between sulfate and sulfide is also demonstrated in all other Icelandic geothermal systems studied.  相似文献   

12.
Variations in sulfur mineralogy and chemistry of serpentinized peridotites and gabbros beneath the Lost City Hydrothermal Field at the southern face of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) were examined to better understand serpentinization and alteration processes and to study fluid fluxes, redox conditions, and the influence of microbial activity in this active, peridotite-hosted hydrothermal system. The serpentinized peridotites are characterized by low total sulfur contents and high bulk δ34S values close to seawater composition. Low concentrations of 34S-enriched sulfide phases and the predominance of sulfate with seawater-like δ34S values indicate oxidation, loss of sulfide minerals and incorporation of seawater sulfate into the serpentinites. The predominance of pyrite in both serpentinites and gabbros indicates relatively high fO2 conditions during progressive serpentinization and alteration, which likely result from high fluid fluxes during hydrothermal circulation and evolution of the Lost City system from temperatures of ∼250 to 150 °C. Sulfate and sulfide minerals in samples from near the base of hydrothermal carbonate towers at Lost City show δ34S values that reflect the influence of microbial activity. Our study highlights the variations in sulfur chemistry of serpentinized peridotites in different marine environments and the influence of long-lived, moderate temperature peridotite-hosted hydrothermal system and high seawater fluxes on the global sulfur cycle.  相似文献   

13.
《International Geology Review》2012,54(14):1635-1648
The Koushk zinc–lead deposit in the central part of the Zarigan–Chahmir basin, central Iran, is the largest of several sedimentary–exhalative (SEDEX) deposits in this basin, including the Chahmir, Zarigan, and Darreh-Dehu deposits. The host-rock sequence consists of carbonaceous, fine-grained black siltstone with interlayered rhyolitic tuffs. It corresponds to the upper part of the Lower Cambrian volcano-sedimentary sequence that was deposited on the Posht-e-Badam Block due to back-arc rifting of the continental margin of the Central Iranian Microcontinent. This block includes the late Neoproterozoic metamorphic basement of the Iran plate, overlain by rocks dating from the Early Cambrian to the Mesozoic. Based on ore body structure, mineralogy, and ore fabric, we recognize four different ore facies in the Koushk deposit: (1) a stockwork/feeder zone, consisting of a discordant mineralization of sulphides forming a stockwork of sulphide-bearing dolomite (quartz) veins cutting the footwall sedimentary rocks; (2) a massive ore/vent complex, consisting of massive replacement pyrite, galena, and sphalerite with minor arsenopyrite and chalcopyrite; (3) bedded ore, with laminated to disseminated pyrite, sphalerite, and galena; and (4) a distal facies, with minor disseminated and laminated pyrite, banded cherts, and disseminated barite. Carbonatization and sericitization are the main wall-rock alterations; alteration intensity increases towards the feeder zone. The δ34S composition of pyrite, sphalerite, and galena ranges from?+6.5 to?+36.7‰. The highest δ34S values correspond to bedded ore (+23.8 to?+36.7‰) and the lowest to massive ore (+6.5 to?+?17.8‰). The overall range of δ34S is remarkably higher than typical magmatic values, suggesting that sulphides formed from the reduction of seawater sulphate by bacteriogenic sulphate reduction in a closed or semi-closed system in the bedded ore, whereas thermochemical sulphate reduction likely played an important role in the feeder zone. Sulphur isotopes, along with sedimentological, textural, mineralogical, and geochemical evidences, suggest that this deposit should be classified as a vent-proximal SEDEX ore deposit.  相似文献   

14.
Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because 34S/32S ratios of vent fluid H2S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different Δ33S (≡δ33S-0.515 δ34S) values of up to 0.04‰ even if δ34S values are identical. Detection of such small Δ33S differences is technically feasible by using the SF6 dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006‰ (2σ).Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H2S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10°N, 13°N, and 21°S and Mid-Atlantic Ridge (MAR) 37°N yield Δ33S values ranging from −0.002 to 0.033 and δ34S from −0.5‰ to 5.3‰. The combined δ34S and Δ33S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13°N and marcasite from MAR 37°N are in isotope disequilibrium not only in δ34S but also in Δ33S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low Δ33S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that 33S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles.  相似文献   

15.
The Sawuershan region, one of the important gold metallogenic belts of Xinjiang, is located in the western part of the Kalatongke island arc zone of north Xinjiang, NW China. There are two gold deposits in mining, namely the Kuoerzhenkuola and the Buerkesidai deposits. Gold ores at the Kuoerzhenkuola deposit occur within Carboniferous andesite and volcanic breccias in the form of gold‐bearing quartz–pyrite veins and veinlet groups containing native gold, electrum, pyrite, pyrrhotite and chalcopyrite. Gold ores at the Buerkesidai deposit occur within Carboniferous tuffaceous siltstones in the form of gold‐bearing quartz veinlet groups and altered rocks, with electrum, pyrite and arsenopyrite as major metallic minerals. Both gold deposits are hosted by structurally controlled faults associated with intense hydrothermal alteration. The typical alteration assemblage is sericite + chlorite + calcite + quartz, with an inner pyrite–sericite zone and an outer chlorite–calcite–epidote zone between orebodies and wall rocks. δ34S values (0.3–1.3‰) of pyrite of ores from Kuoerzhenkuola deposit are similar to those (0.4–2.9‰) of pyrite of ores from Buerkesidai deposit. δ34S values (1.1–2.8‰) of pyrite from altered rocks are similar to δ34S values of magmatic or igneous sulfide sulfur, but higher than those from ores. 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb data of sulfide from ores range within 17.72–18.56, 15.34–15.61, and 37.21–38.28, respectively. These sulfur and lead isotope compositions imply that ore‐forming materials might originate from multiple, mainly deep sources. He and Ar isotope study on fluid inclusions of pyrites from ores of Kuoerzhenkuola and Buerkesidai gold deposits produces 40Ar/36Ar and 3He/4He ratios in the range of 282–525 and 0.6–9.4 R/Ra, respectively, indicating a mixed source of deep‐seated magmatic water (mantle fluid) and shallower meteoric water. In terms of tectonic setting, the gold deposits in the Sawuershan region can be interpreted as epithermal. These formations resulted from a combination of protracted volcanic activity, hydrothermal fluid mixing, and a structural setting favoring gold deposition. Fluid mixing was possibly the key factor resulting in Au deposition in the gold deposits in Sawuershan region.  相似文献   

16.
The Benue Trough of Nigeria is an intracratonic rift basin hosting several vein-type base metal deposits. The Akiri Cu ± (Ag) deposit represents a distinct sub-class of sediment-hosted Pb-Zn-Cu-Ba mineralization found throughout the Benue Trough. The deposit is hosted in bleached red beds of the Keana Formation and in shale-siltstones and carbonates of the Ezeaku Formation in the Middle Benue Trough, North-Central Nigeria. Mineralization at the Akiri deposit occurs as vein in-fillings in a series of NE-SW and E-W trending faults and fractures in the Early- to Late-Turonian Keana and Eze-Aku sedimentary rocks. To better constrain the sources of ore minerals and structural controls on the formation of this sediment-hosted Cu ± (Ag) mineralization, we report combined geologic, geochemical, mineralogical, and stable isotopic data for the Akiri Cu ± (Ag) deposit. Major ore-stage sulfides at Akiri are chalcopyrite and pyrite, which were accompanied by several types of alteration, including silicification, hematization, limited pyritization, and bleaching of mineralized sandstone bodies. In-situ trace element and sulfur isotopic data distinguishes early-stage pyrite (Py1) from late-stage pyrite (Py2). The late-stage Py2 co-exists with chalcopyrite suggesting coeval precipitation. Early-stage pyrite (Py1) contains lower Ag (avg. 0.04 ppm) but higher Au (avg. 3.03 ppm) than the late-stage pyrite (Py2) (avg. Ag = 2.78 ppm; Au = 0.424 ppm). The δ34S values of the early-stage sulfide (Py1) vary from 19.07‰ to 25.99‰ (avg. 22.20‰), suggesting that sulfur was largely derived from thermochemical reduction (TSR) of seawater sulfate. The δ34S values for co-existing Py2 and chalcopyrite range from 9.83‰ to 11.24‰ (avg. 10.32‰) and from 7.37‰ to 10.69‰ (avg. 8.96‰), respectively, suggesting a derivation of sulfur from TSR of seawater sulfate with contributions from magmatic sulfur. Based on structural features and ore textures, we propose that sulfide precipitation at Akiri was facilitated by sulfur-rich fluids circulating through pre-existing structures (fractures and faults) under fairly high (>200 °C) to moderate (<170 °C) temperature conditions. Geological, mineralogical, geochemical and isotopic data from this study support the classification of the Akiri Cu (+Ag) deposit as an epigenetic sandstone-hosted copper deposit.  相似文献   

17.
The Huangshilao gold deposit (>13.5 t Au) is comprised of stratabound pyrite‐dominant massive sulfide ores, and is distinguished from the skarn Cu, Au, and Cu–Au deposits that are dominant in the Tongguanshan orefield, Tongling, east‐central China. The stratabound orebodies are situated along flexural slip faults along the unconformity between the Upper Devonian Wutong and the Upper Carboniferous Huanglong Formations. The ores, dominated by crystallized pyrite, colloform pyrite, and pyrrhotite, are systematically sampled from the underground stopes along strike drifts. The δ34S values of ore sulfides yield a wide variation from ?11.3 to 11.4‰, but mostly within 4–8‰, corresponding to the δ34S range (3.4–8.7‰) of the Yanshanian Tongguanshan and Tianshan quartz diorite intrusions in the Tongguanshan orefield, suggesting a magmatic dominated sulfur source. Few obvious negative δ34S values are induced by an involvement of sedimentation‐related biogenic sulfur. The wide δ34S variation denotes an incongruent physical and chemical interaction of the two sources. Combined analysis of gold contents and sulfur isotopes of the sulfides show that the magmatic hydrothermal solution provides primary metals despite a small quantity that may have been contributed by the sedimentary pyrites. The hydrothermal alteration, thermal metamorphism, trace element concentration in pyrites, and existing aeromagnetic data jointly suggest that the hydrothermal fluid migrated vertically from an intrusion below, along the flexural slip faults, but not laterally from the nearby outcrop of Tianshan stock.  相似文献   

18.
This study examines the rare-earth-elemenl and isotopic geochemistry of sulfide ores and associated rocks in the Bajiazi sulfide deposits of northeastern China. The distribution and concentration of rare earth elements (REE) in sulfide ores and associated rocks from the Bajiazi deposits have been determined by inductively coupled plasma spectroscopy (ICP) methods. Birdwing-shaped rare-earth-element profiles are only observed in granitic rocks at Bajiazi. Diverse rare-earth-element profiles of the ores and dolostones are different from those of granite and are interpreted to reflect an early sedimentary-diagenetic mineralization stage during which rare earth elements were added to the ores and host rocks. The characteristic features of the abundances of REE in the Bajiazi samples, including granite and sedimentary host rocks, are demonstrated by a variety of Eu anomalies in the chondrite-normalized REE pattern. Eu is the most mobile element, exhibiting increasingly negative anomalies in granite rock samples relative to the depletion of the sulfide ores and associated sedimentary host rocks, which are considered to be caused by preferential scavenging of Eu from sea water to sediments.

The δ34S values of sulfide minerals at Bajiazi generally range from ?12.3 to 14.2%, suggesting reduction both of marine sulfate and biogenic sources. The δ34S values from different ore types, sulfide minerals, and mines indicate a sedimentary exhalative origin, although they were, to some extent, homogenized during late overprinting. The late-stage sulfides from Bajiazi are isotopieally remarkably homogeneous and are significantly, although slightly, enriched in δ34S. These results imply multiple sources of sulfur derived from biogenic reduction, and/or sulfate in oceanic and/or connate waters, or from marine evaporites, and/or from magmatic hydrothermal sources. Isotopic temperatures from intersulfide fractionations (pyrite, sphalerite, and galena) range from 75° to 542°C, indicating the Bajiazi sulfide minerals have experienced different mineralizing stages.

Galena in the Bajiazi Proterozoic sediment-hosted Pb-Zn sulfide deposits has a very uniform Pb-isotope composition, with 206Pb/204Pb = 16.07 to 16.58, 207Pb/204Pb = 15.00 to 15.66, and 208Pb/204Pb = 36.13 to 36.92, suggesting that it all formed from a common mineralizing fluid. The variation of lead-isotopic values of ores is similar to that of their host sedimentary strata. The lead in the various ore types and host rocks within the Bajiazi district is virtually identical. Lead-isotope signatures, which generally plot very close to model crustal growth curves, characterized by a model age of ～1350 Ma, indicate a normal, nonradiogenic origin and an Early Proterozoic upper-crustal source for the lead in the ores. That lead was unrelated to the radiogenic lead in the Mesozoic granite.

The δ13C values range from +1 to ?5% PDB, and the δ18O values from ?6 to ?15% PDB. Later crystallization generations are enriched in the light isotopes of carbon and oxygen compared to early generations. The characteristics of carbon and oxygen isotopes of the Bajiazi deposits indicate that: (1) primary ores were precipitated in the Proterozoic marine environment; (2) both ores and host carbonates from the Bajiazi district are remarkably homogeneous in their carbon- and oxygen-isotope compositions during later tectonic, conlact-metamorphic stages; (3) although the variations in isotopic composition of carbon and oxygen are relatively small, a significant evolution toward a lighter isotopic composition with advancing diagenetic, tectonic, and contact metamorphic processes is observed; and (4) this evolution is independent of the presence or absence of ore minerals.  相似文献   

19.
The source of sulfur in giant Norilsk-type sulfide deposits is discussed. A review of the state of the problem and a critical analysis of existing hypotheses are made. The distribution of δ34S in sulfides of ore occurrences and small and large deposits and in normal sedimentary, metamorphogenic, and hypogene sulfates is considered. A large number of new δ34S data for sulfides and sulfates in various deposits, volcanic and terrigenous rocks, coals, graphites, and metasomatites are presented. The main attention is focused on the objects of the Norilsk and Kureika ore districts. The δ34S value varies from -14 to + 22.5‰ in sulfides of rocks and ores and from 15.3 to 33‰ in anhydrites. In sulfide-sulfate intergrowths and assemblages, δ34S is within 4.2-14.6‰ in sulfides and within 15.3-21.3‰ in anhydrites. The most isotopically heavy sulfur was found in pyrrhotite veins in basalts (δ34S = 21.6‰), in sulfate veins cutting dolomites (δ34S = 33‰), and in subsidence caldera sulfates in basalts (δ34S = 23.2-25.2‰). Sulfide ores of the Tsentral’naya Shilki intrusion have a heavy sulfur isotope composition (δ34S = + 17.7‰ (n = 15)). Thermobarogeochemical studies of anhydrites have revealed inclusions of different types with homogenization temperatures ranging from 685 °C to 80 °C. Metamorphogenic and hypogene anhydrites are associated with a carbonaceous substance, and hypogene anhydrites have inclusions of chloride-containing salt melts. We assume that sulfur in the trap sulfide deposits was introduced with sulfates of sedimentary rocks (δ34S = 22-24‰). No assimilation of sulfates by basaltic melt took place. The sedimentary anhydrites were “steamed” by hydrocarbons, which led to sulfate reduction and δ34S fractionation. As a result, isotopically light sulfur accumulated in sulfides and hydrogen sulfide, isotopically heavy sulfur was removed by aqueous calcium sulfate solution, and “residual” metamorphogenic anhydrite acquired a lighter sulfur isotope composition as compared with the sedimentary one. The wide variations in δ34S in sulfides and sulfates are due to changes in the physicochemical parameters of the ore-forming system (first of all, temperature and Pch4) during the sulfate reduction. The regional hydrocarbon resources were sufficient for large-scale ore formation.  相似文献   

20.
More than 200 analyses of the sulfur isotopic composition of sulfides from various terrigenous and intrusive host rocks, metasomatically altered wall rocks, and gold lodes of the Upper Kolyma region are presented. In accessory pyrite of the metaterrigenous rocks, δ34S varies from ?23.1 to +5.7‰ δ34S of pyrite and arsenopyrite from gold-quartz mineralization is within the range ?10.6 to ?0.4‰ and is close to the average δ34S of pyrite from the metaterrigenous rocks (?4.4‰). In the intrusive rocks, δ34S of pyrite varies from ?3.8 to +2.6‰ (+0.7‰, on average) and drastically differs from δ34S of arsenopyrite from postmagmatic gold-rare-metal mineralization (?7.9 to ?2.7‰; ?5.2‰, on average). The comparison of the δ34S of accessory sulfides from the host rocks with δ34S of sulfides from the gold deposits suggests that sulfur mobilized from the terrigenous sequences participated in the hydrothermal process. The results obtained are consistent with the metamorphic model of the formation of gold-quartz deposits in the Upper Kolyma region.  相似文献   

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