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1.
Jurassic high-sulfur coals from the Maghara area in Egypt were analyzed for the abundance and isotopic composition of different forms of sulfur. Analyses indicated that the sulfur occurs in the form of organic, pyrite, and sulfate forms. Pyrite sulfur represents the major fraction, while sulfate sulfur is minor and could be formed during sample preparation for the analyses.The δ34S CDT values of the organic sulfur are positive ranging between 1.0‰ and 13.5‰ with an average of 9.1‰. Pyrite δ34S values are also positive ranging between 1.5‰ and 15.4‰ with an average of 6.6‰. The high δ34S values of the organic sulfur in the Maghara coals suggest a freshwater origin of the organic components of these coals. The lack of correlation between pyrite and organic sulfur isotopes implies different incorporation mechanisms of sulfur. The high-sulfur contents along with the positive and high δ34S values suggest a marine origin of pyrite sulfur and support the geological interpretation of marine invasion after the peat formation that was responsible for the incorporation of the pyrite sulfur.The occurrence of pyrite as euhedral crystals as well as the high and positive δ34S values of the pyrite sulfur indicates the formation of pyrite during diagenesis as a result of marine water invasion of the preexisting peat in a brackish coastal plain environment.  相似文献   

2.
Large rounded pyrite grains (>1 mm), commonly referred to as “buckshot” pyrite grains, are a characteristic feature of the auriferous conglomerates (reefs) in the Witwatersrand and Ventersdorp supergroups, Kaapvaal Craton, South Africa. Detailed petrographic analyses of the reefs indicated that the vast majority of the buckshot pyrite grains are of reworked sedimentary origin, i.e., that the pyrite grains originally formed in the sedimentary environment during sedimentation and diagenesis. Forty-one of these reworked sedimentary pyrite grains from the Main, Vaal, Basal, Kalkoenkrans, Beatrix, and Ventersdorp Contact reefs were analyzed for their multiple sulfur isotope compositions (δ34S, Δ33S, and Δ36S) to determine the source of the pyrite sulfur. In addition, five epigenetic pyrite samples (pyrite formed after sedimentation and lithification) from the Middelvlei and the Ventersdorp Contact reefs were measured for comparison. The δ34S, Δ33S, and Δ36S values of all 41 reworked sedimentary pyrite grains indicate clear signatures of mass-dependent and mass-independent fractionation and range from ?6.8 to +13.8?‰, ?1.7 to +1.7?‰, and ?3.9 to +0.9?‰, respectively. In contrast, the five epigenetic pyrite samples display a very limited range of δ34S, Δ33S, and Δ36S values (+0.7 to +4.0?‰, ?0.3 to +0.0?‰. and ?0.3 to +0.1?‰, respectively). Despite the clear signatures of mass-independent sulfur isotope fractionation, very few data points plot along the primary Archean photochemical array suggesting a weak photolytic control over the data set. Instead, other factors command a greater degree of influence such as pyrite paragenesis, the prevailing depositional environment, and non-photolytic sulfur sources. In relation to pyrite paragenesis, reworked syngenetic sedimentary pyrite grains (pyrite originally precipitated along the sediment-water interface) are characterized by negative δ34S and Δ33S values, suggesting open system conditions with respect to sulfate supply and the presence of microbial sulfate reducers. On the contrary, most reworked diagenetic sedimentary pyrite grains (pyrite originally precipitated below the sediment-water interface) show positive δ34S and negative Δ33S values, suggesting closed system conditions. Negligible Δ33S anomalies from epigenetic pyrite suggest that the sulfur was sourced from a mass-dependent or isotopically homogenous metamorphic/hydrothermal fluid. Contrasting sulfur isotope compositions were also observed from different depositional environments, namely fluvial conglomerates and marine-modified fluvial conglomerates. The bulk of the pyrite grains from fluvial conglomerates are characterized by a wide range of δ34S values (?6.2 to +4.8?‰) and small Δ33S values (±0.3?‰). This signature likely represents a crustal sulfate reservoir derived from either volcanic degassing or from weathering of sulfide minerals in the hinterland. Reworked sedimentary pyrite grains from marine-modified fluvial conglomerates share similar isotope compositions, but also produce a positive Δ33S/δ34S array that overlaps with the composition of Archean barite, suggesting the introduction of marine sulfur. These results demonstrate the presence of multiple sources of sulfur, which include atmospheric, crustal, and marine reservoirs. The prevalence of the mass-dependent crustal sulfur isotope signature in fluvial conglomerates suggests that sulfate concentrations were probably much higher in terrestrial settings in comparison to marine environments, which were sulfate-deficient. However, the optimum conditions for forming terrestrial sedimentary pyrite were probably not during fluvial progradation but rather during the early phases of flooding of low angle unconformities, i.e., during retrogradational fluvial deposition, coupled in some cases with marine transgressions, immediately following inflection points of maximum rate of relative sea level fall.  相似文献   

3.

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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4.
The Ana Yatak massive sulfide deposit is located in the Ergani-Maden District of southeastern Turkey and has been a major source of copper for more than 4,000 years. The mineralization is hosted by strongly chloritized serpentinite, gabbro, diabase, and mud-stone. The ore body is ～600 × 250 m in maximum dimension, mainly consists of pyrite and chalcopyrite, and locally contains abundant magnetite, pyrrhotite, and chromite. The gangue contains predominantly chlorite, rarely quartz. This paper is mainly concerned with an investigation of the sulfur-isotope systematics of the Ana Yatak deposit.

Pyrite and chalcopyrite from the ore and pyrite from the host rocks were sampled and analyzed to determine their δ34S composition. δ34S values were found to vary within the range from +4.5 to + 9.3‰ for pyrites (mean δ34S = + 6.5 ± 1.8) and from +4.5 to +10.0 for chalcopyrites (mean δ34S = +6.7 ± 1.9) of the ore, and from +5.8 to +8.8 for pyrites (mean δ34S = + 7.3 ± 1.3) of the host rock. The δ34S compositions of all samples were found to vary from +4.5 to +10.0‰. For the chalcopyrite-pyrite pairs, there is a clear relationship of approximately equal δ34S values at each sampling site. Frequency distribution of the δ34S values is not unimodal and exhibits two peaks. The range of sulfur-isotope systematics implies that the Ana Yatak mineralization was influenced to a greater extent by seawater than by hydrothermal fluids.  相似文献   

5.
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   

6.
Petrographic and sulphur isotope studies support the long‐held contention that rounded grains of pyrite in siliciclastic sequences of the Late Archaean Witwatersrand Supergroup originated as placer grains. The grains are concentrated at sites where detrital heavy minerals are abundant within quartz‐pebble conglomerates and quartzose sandstones. Depositional sites with abundant pyrite are: (1) within the matrix of bar‐type, clast‐supported conglomerates; (2) on scoured or winnowed surfaces; and (3) on stratification planes. The grains are internally compact or porous, with truncation of internal structure at outer margins indicating fragmentation and rounding of pyritic source‐rocks during erosion and sediment transport. A large range in textures reflects source‐rock lithologies, with known varieties linked to sedimentary‐hosted diagenetic pyrite, volcanic‐hosted massive sulphide deposits and hydrothermal pyrite. Laser ablation sulphur isotope analysis of pyrite reveals a broader range in δ34S values (? 5·3 to + 6·7‰) than that of previously reported conventional bulk‐grain analyses (? 1 to + 4‰). Rounded pyrite from the Steyn Reef has significant variation in δ34S values (? 4·7 to + 6·7‰) that establishes heterogeneous sulphur compositions, with even adjacent grains having diverse isotopic signatures. The heterogeneity supports a placer origin for rounded pyrite. Euhedral pyrite and pyrite overgrowths which are undoubtedly authigenic have restricted δ34S values (? 0·5 to + 2·5‰), are chemically distinct from rounded pyrite and are probably the products of metamorphism or hydrothermal alteration. The placer origin of rounded pyrite indicates that pyrite was a stable heavy mineral during erosion and transport in the early atmosphere. Its distribution in three sequences (Witwatersrand Supergroup, Ventersdorp Contact Reef and Black Reef), and in other sequences not linked to Witwatersrand‐type Au‐U ore deposits, implies deposition of redox‐sensitive detrital heavy minerals during the Late Archaean. Consequently, rounded grains of detrital pyrite are strong indicators of an oxygen‐poor atmosphere. While not confirming a placer origin for gold in Witwatersrand Au‐U ore deposits, the palaeoenvironmental significance of rounded pyrite negates its link to hydrothermal mineralization.  相似文献   

7.
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   

8.
The Navia gold belt is located in the West Asturian-Leonese Zone of the Iberian Variscan Orogen. The host rocks of the mineralization are quartzites, sandstones and black shales of Cambro-Ordovician age. The gold belt extends along 35 km and has five major veins: Penedela, Encarnita, Fornaza, Carmina and S. Jose. The ores belong to at least four associations having contrasting mineralogies and textures. The δ34S values for individual mineral phases reflect the polyphase metallogenic history. The older association (Stage 1) is Fe-Mn-rich and is made up of spessartine, grunerite-dannemorite and quartz, with magnetite, pyrrhotite and chalcopyrite as metallic phases. The mineralization of Stage 1 is followed by the As-rich Stage 2 with quartz, arsenopyrite and pyrite. The δ34S values for pyrite range from 14.9 to 19.9 per mil (n = 16), and for arsenopyrite from 13.2 to 17.3 per mil (n = 7). The observed isotopic homogeneity likely implies isotopic equilibrium at the scale of the gold vein. Stage 3 contains a coarse-grained base metal sulphide-rich association. The δ4S values for sphalerite range from 16.4 to 20.6 per mil (n= 16), and for galena from 17.0 to 18.7 per mil (n = 11). δ34Ssp > δ34Sgl suggests that the sulphur isotopic fractionation of the ore-forming system had reached equilibrium. The youngest crosscutting mineral association (Stage 4) consists of Pb-Sb sulphosalts, bornite, electrum and quartz. The δ34S values for sulphosalts range from 9.7 to 15.8 per mil, showing the lightest results of the Navia sulphides.The relatively tight clustering of δ34S values of the Au-related sulphides, and the results of fluid inclusions and paragenetic studies, can be interpreted to indicate that the hydrothermal fluids of the last three stages were dominated by H2S. In the H2S predominant field, sulphide minerals precipitating from solutions would exhibit δ34S values similar to the δ34SΣS value of the ore fluid. The heavy δ34SΣS of the Navia fluids is consistent with leaching of sulphur from the host rocks. The main sulphur source could be diagenetic pyrite from the siliciclastic rocks of the Cabos and Luarca Formations, which exhibit δ34S values from 8.3 to 21.2 per mil. An additional sulphur-source in Stage 3 would be the leaching of disseminated sphalerite and galena present in Cambrian carbonates.  相似文献   

9.
Acid sulfate-chloride thermal water samples collected together with fumarolic gases from various volcanic areas in northeastern Japan were studied chemically and isotogdically. δ34S (COT) values of sulfate and hydrogen sulfide from these volcanic hot springs range from +4.0 to +31 and from ?15.0 to ?2.0% respectively, with δ34Sys value of +2.5 to +31. The δ34S of the sulfate in the more saline waters tends to become smaller with increasing ratio of SO4 to Cl, although the chemical and isotopic composition of acid thermal water within some areas may be altered by secondary processes during the discharge of the thermal waters. This trend can be explained by the reaction of the volcanic gases, having S/Cl of 4 ~ 7 and total sulfur of ~0% in δ34S, with ground water at 200°C, and/or the removal of sulfide phase depleted in 34S from the acid thermal water formed by the disproportionation of volcanic sulfur. The sulfur species in acid sulfate-chloride thermal water are shown to be volcanic exhalations.  相似文献   

10.
Abstract. Sulfur isotope ratios of cinnabar from Hg deposits and stibnite, jamesonite and berthierite from Sb deposits in Japan are examined in order to understand metallogeneses of Hg and Sb deposits in Japanese island arcs. The studied Hg and Sb deposits include the Hg deposit at Yamato‐suigin (Honshu) and the Sb deposit at Ichinokawa (Shikoku) in the Southwest Japan arc. In addition, Hg deposits including Itomuka and Ryushoden in central Hokkaido and Hg and Sb mineralizations in Northeast Japan arc are examined. The δ34S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, including the Itomuka and Ryushoden deposits range widely, from ‐10 to +16 %o, the highest values encountered at the Samani deposit. The δ34S values of cinnabar from other areas in Japan range from ‐12 to +5 %o, having δ34S values higher than +2 %o from southwestern Hokkaido (Meiji deposit), Shikoku (Suii deposit) and Kyushu (Hasami and Yamagano deposits). On the other hand, the δ34S values of stibnite from all areas in Japan range from ‐14 to +5 %o, having positive δ34S values higher than +2 %o up to +5 %o from southwestern Hokkaido (Yakumo, Toyotomi and Teine deposits) and eastern‐central Honshu (Hachiman and Daikoku deposits). The variation in δ34S values of Hg and Sb deposits may reflect the variation in δ34S values of country rocks or variation in mixing ratio of sulfur extracted from the country rocks, sulfur derived from seawater sulfate, and sulfur derived from magmatic emanations. The relatively high δ34S values of cinnabar and stibnite higher than +2 %o from southwestern Hokkaido, eastern‐central Honshu and Kyushu are probably caused by contribution of volcanic emanation from arc magmas having positive σδ34S values, whereas the positive δ34S values of cinnabar higher than +2 %o from Suii deposit in Shikoku may be attributed to structurally substituted sulfate in limestone country rocks and/or sulfur derived from seawater sulfate. However, the wide range of the δ34S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, is difficult to explain at this moment. Other relatively low, negative δ34S values of cinnabar and stibnite, berthierite from other areas in Japan may be attributed to 1) incorporation of isotopically light sedimentary sulfur or sulfur derived from ilmenite‐series silicic magma, or 2) less contribution of volcanic emanation from arc magmas having positive σδ34S values.  相似文献   

11.
Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in 34S during thermal maturation compared with the initial δ34S values. The δ34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ34S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen δ34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite.  相似文献   

12.
In the Eastern Pontide Region of northeastern Turkey, volcanogenic Cu-Zn-Pb deposits of the Kuroko type are widespread within the dacitic series of the Liassic-Eocene volcano-sedimentary succession. Sulfide mineralization within the studied deposits shows four different depositional styles: disseminated ore; polymetallic stockwork ores; polymetallic massive ores; and disseminated pyrite in the hanging-wall tuff units. Only the stockwork and massive ores are economically important, and usually one or the other dominates in each ore body.

The δ34S of sulfide minerals belonging to the various styles of mineralization are in the range from ?2.6 to +5.2% (VCDT): pyrite has the highest values and the galena lowest values in agreement with the usual isotopic-fractionation trends. Massive ores have heavier sulfur-isotope composition among the mineralization styles and the heaviest values are recorded in barite- and gypsum-rich deposits. The close similarity of the δ34S among the various mineralization episodes in some deposits indicates a single sulfur source having a stable and homogenous composition.

The δ34S of sulfates fall into three groups: barites and primary gypsum (15.4 to 20.4%), close to coeval seawater sulfate; one value of barite (25.4%) heavier than coeval sea water; and values of secondary gypsum (2.2 to 8.0%) either very light compared to coeval seawater sulfate, or within the range recorded from sulfide minerals. The δ34S values of pyrite disseminated in the brecciated dacite tuff units are very close to zero and similar to the ones reported for magmatic rocks, suggesting a magmatic source for the sulfur of the earliest sulfide mineralization episode. These δ34S data are not sufficient to calculate the fraction of the reduced sulfur derived from seawater sulfate, as the associated fractionation factor cannot be constrained.  相似文献   

13.
近年来,在相山铀矿田的西部牛头山地区深部发现了铅锌矿化体,其成因机制不明.为探讨牛头山铅锌矿化体物质来源,开展了硫化物原位硫同位素分析研究.根据硫化物矿物之间的充填和包裹关系判断,铅锌矿化体金属硫化物形成的先后顺序是:黄铁矿形成最早,方铅矿和闪锌矿次之,细脉状黄铜矿形成最晚.利用LA-MC-ICP-MS技术对矿化体中几种金属硫化物分别进行了系统的原位硫同位素分析.结果显示:黄铁矿、闪锌矿、方铅矿、细脉状黄铜矿的δ34S值介于-4.8‰~+5.4‰之间,各硫化物矿物之间硫同位素未达到完全平衡分馏,利用黄铁矿δ34S值得到的矿化流体δ34SΣS值（总硫同位素组成）近似为+3.7‰,与共生矿物对（闪锌矿-方铅矿）图解法得到的闪锌矿和方铅矿沉淀时矿化流体的δ34SΣS值（+3.2‰）相近,表明形成牛头山铅锌矿化体的矿化流体δ34SΣS值大约为+3.7‰,为岩浆硫.结合前人的岩浆岩年龄数据,我们判断该铅锌矿化体金属硫化物的硫可能主要来自次火山岩相花岗斑岩岩浆热液.同一薄片中闪锌矿δ34S值高于共生的方铅矿,表明两者硫同位素基本平衡,利用共生矿物对（闪锌矿-方铅矿）硫同位素温度计计算得出平衡温度为197~476℃,与前人通过脉石矿物流体包裹体得到的铅锌矿化流体温度基本一致.相山火山盆地与相邻的北武夷黄岗山、梨子坑等产铅锌矿的火山盆地具有相似的成矿条件及成矿物质来源,使相山火山盆地具有良好的铅锌多金属找矿前景.   相似文献   

14.
δ34S values of pyrite, molybdenite and chalcopyrite were determined from the Malanjkhand copper deposit. These minerals constitute the primary sulfide phases that were deposited after the initial magnetite deposition in the main orebody and host granitoid. Pyrite exhibits a depleted range of values (?2.63 to ?0.56‰), chalcopyrite, a very narrow range of values around zero (?0.039 to 0.201‰) and molybdenite furnishes a range of enriched values (0.68 to 1.98‰). On back calculation of the δ34S values of H2S in the fluid from which the minerals were likely to have precipitated, using standard expressions for equilibrium fractionation at the temperature range obtained from fluid inclusion and mineral fluid equilibria, it is observed that H2S in the fluid at pyrite deposition was depleted and gradually became enriched towards molybdenite and chalcopyrite deposition. This trend is best explained as being due to inorganic reduction of SO42? in the fluid and is very much in agreement with the paragenetic sequence indicating increasing activity of H2S in the fluid. The very restricted range in the δ34S values of sulfide minerals in the fluid does indicate a single, possibly magmatic, source of sulfur that also agrees well with the earlier deduced model of genesis of the deposit as an ancient geothermal system associated with granitic magmatism.  相似文献   

15.
The 13.1-Moz high-sulfidation epithermal gold deposit of Lagunas Norte, Alto Chicama District, northern Peru, is hosted in weakly metamorphosed quartzites of the Upper Jurassic to Lower Cretaceous Chimú Formation and in overlying Miocene volcanic rocks of dacitic to rhyolitic composition. The Dafne and Josefa diatremes crosscut the quartzites and are interpreted to be sources of the pyroclastic volcanic rocks. Hydrothermal activity was centered on the diatremes and four hydrothermal stages have been defined, three of which introduced Au ± Ag mineralization. The first hydrothermal stage is restricted to the quartzites of the Chimú Formation and is characterized by silice parda, a tan-colored aggregate of quartz-auriferous pyrite–rutile ± digenite infilling fractures and faults, partially replacing silty beds and forming cement of small hydraulic breccia bodies. The δ34S values for pyrite (1.7–2.2?‰) and digenite (2.1?‰) indicate a magmatic source for the sulfur. The second hydrothermal stage resulted in the emplacement of diatremes and the related volcanic rocks. The Dafne diatreme features a relatively impermeable core dominated by milled slate from the Chicama Formation, whereas the Josefa diatreme only contains Chimú Formation quartzite clasts. The third hydrothermal stage introduced the bulk of the mineralization and affected the volcanic rocks, the diatremes, and the Chimú Formation. In the volcanic rocks, classic high-sulfidation epithermal alteration zonation exhibiting vuggy quartz surrounded by a quartz–alunite and a quartz–alunite–kaolinite zone is observed. Company data suggest that gold is present in solid solution or micro inclusions in pyrite. In the quartzite, the alteration is subtle and is manifested by the presence of pyrophyllite or kaolinite in the silty beds, the former resulting from relatively high silica activities in the fluid. In the quartzite, gold mineralization is hosted in a fracture network filled with coarse alunite, auriferous pyrite, and enargite. Alteration and mineralization in the breccias were controlled by permeability, which depends on the type and composition of the matrix, cement, and clast abundance. Coarse alunite from the main mineralization stage in textural equilibrium with pyrite and enargite has δ34S values of 24.8–29.4?‰ and $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ values of 6.8–13.9?‰, consistent with H2S as the dominant sulfur species in the mostly magmatic fluid and constraining the fluid composition to low pH (0–2) and logfO2 of ?28 to ?30. Alunite–pyrite sulfur isotope thermometry records temperatures of 190–260 °C; the highest temperatures corresponding to samples from near the diatremes. Alunite of the third hydrothermal stage has been dated by 40Ar/39Ar at 17.0?±?0.22 Ma. The fourth hydrothermal stage introduced only modest amounts of gold and is characterized by the presence of massive alunite–pyrite in fractures, whereas barite, drusy quartz, and native sulfur were deposited in the volcanic rocks. The $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ values of stage IV alunite vary between 11.5 and 11.7?‰ and indicate that the fluid was magmatic, an interpretation also supported by the isotopic composition of barite (δ34S?=?27.1 to 33.8?‰ and $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ ?=?8.1 to 12.7?‰). The Δ34Spy–alu isotope thermometry records temperatures of 210 to 280 °C with the highest values concentrated around the Josefa diatreme. The Lagunas Norte deposit was oxidized to a depth of about 80 m below the current surface making exploitation by heap leach methods viable.  相似文献   

16.
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   

17.
Multiple sulfur isotope ratios （^34S/^33S/^32S） of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; 633S = -0.7%o to 3.8‰,δ^34S = 0.1‰-8.8‰, △^33S = -2.3‰ to -0.7‰. The sulfur isotope compositions show obvious mass-independent fractionation （MIF） signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5 PAL （the present atmosphere level）. The sulfate produced by photolysis of SO2 with negative △^33S precipitated near the volcanic activity center; and the product of element S with positive △^33S precipitated far away from the volcanic activity center. The lower △^33S values of sulfide （-2.30‰ to --0.25‰） show that Shihezhuang was near the volcanic center, and sulfur was mostly from sulfate produced by photolysis. The higher △^33S values （-0.5‰ to -‰） indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL （mass dependent fractionation line） on the plot of δ^34S--δ^33S, showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.  相似文献   

18.
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   

19.
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   

20.
Sulfur isotopic disequilibrium is commonly observed between associated pyrite and copper sulfides in NW Queensland. A sulfur isotopic study of copper mineralization in dolomites at Paradise Valley and arenites at Mammoth has allowed the significance of such disequilibrium to be evaluated. Copper mineralization at Paradise Valley is characterized by a greater enrichment in 34S, with δ34S values often greater than +30‰, for both copper sulfides and associated syngenetic/diagneetic pyrite. At Mammoth, copper sulfides have isotopic compositions (δ34S=?15.9 to ?0.3‰) transitional between disseminated syngenetic/diagenetic pyrite (δ34S=?5.7 to ?1.7‰) and epigenetic vein pyrite (δ34S=?17.9 to ?7.1‰) suggesting progressive reaction and replacement of syngenetic/diagenetic pyrite by a copper-bearing mineralizing fluid under oxidizing conditions. The isotopic data, within the constraints imposed by geological and geochemical factors, support a model of reaction between copper-bearing mineralizing fluids and pre-existing syngenetic/diagenetic pyrite for both the carbonate- and arenite-hosted deposits.  相似文献   

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