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1.
Greenstone belts contain several clues about the evolutionary history of primitive Earth. Here, we describe the volcano-sedimentary rock association exposed along the eastern margin of the Gavião Block, named the Northern Mundo Novo Greenstone Belt (N-MNGB), and present data collected with different techniques, including U–Pb–Hf–O isotopes of zircon and multiple sulfur isotopes (32S, 33S, 34S, and 36S) of pyrite from this supracrustal sequence. A pillowed metabasalt situated in the upper section of the N-MNGB is 3337 ± 25 Ma old and has zircon with εHf(t) =  ?2.47 to ?1.40, Hf model ages between 3.75 Ga and 3.82 Ga, and δ18O = +3.6‰ to +7.3‰. These isotopic data, together with compiled whole-rock trace element data, suggest that the mafic metavolcanic rocks formed in a subduction-related setting, likely a back-arc basin juxtaposed to a continental arc. In this context, the magma interacted with older Eoarchean crustal components from the Gavião Block. Detrital zircons from the overlying quartzites of the Jacobina Group are sourced from Paleoarchean rocks, in accordance with previous studies, yielding a maximum depositional age of 3353 ± 22 Ma. These detrital zircons have εHf(t) =  ?5.40 to ?0.84, Hf model ages between 3.66 Ga and 4.30 Ga, and δ18O = +4.8‰ to +6.4‰. The pyrite multiple sulfur isotope investigation of the 3.3 Ga supracrustal rocks from the N-MNGB enabled a further understanding of Paleoarchean sulfur cycling. The samples have diverse isotopic compositions that indicate sulfur sourced from distinct reservoirs. Significantly, they preserve the signal of the anoxic Archean atmosphere, expressed by MIF-S signatures (Δ33S between ?1.3‰ to +1.4‰) and a Δ36S/Δ33S slope of ?0.81 that is indistinguishable from the so-called Archean array. A BIF sample has a magmatic origin of sulfur, as indicated by the limited δ34S range (0 to +2‰), Δ33S ~ 0‰, and Δ36S ~ 0‰. A carbonaceous schist shows positive δ34S (2.1‰–3.5‰) and elevated Δ33S (1.2‰–1.4‰) values, with corresponding negative Δ36S between ?1.2‰ to ?0.2‰, which resemble the isotopic composition of Archean black shales and suggest a source from the photolytic reduction of elemental sulfur. The pillowed metabasalt displays heterogeneous δ34S, Δ33S, and Δ36S signatures that reflect assimilation of both magmatic sulfur and photolytic sulfate during hydrothermal seafloor alteration. Lastly, pyrite in a massive sulfide lens is isotopically similar to barite of several Paleoarchean deposits worldwide, which might indicate mass dependent sulfur processing from a global and well-mixed sulfate reservoir at this time.  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 Cipoeiro gold deposit, located in the Gurupi Belt, northern Brazil, is hosted by tonalites of 2148 Ma. The deposit is controlled by splays related to the major strike-slip Tentugal shear zone, and at the deposit scale, the mineralization is confined to ductile–brittle shear zones. Mineralization style comprises thick quartz veins and narrow and discontinuous quartz-carbonate veinlets associated with disseminations in altered host rocks. The postmetamorphic hydrothermal paragenesis is composed of quartz, calcite, chlorite, white mica (phengite), pyrite, and minor albite. Electron microprobe analysis of chlorites reveals a relatively uniform chemical composition at depths of more than 100 m. The chlorites are characterized by (Fe + Mg) ratios between 0.37 and 0.47 and AlIV ranging between 2.22 and 2.59 a.p.f.u. and are classified as Fe-chlinochlore. Temperatures calculated by applying the AlIV contents of chlorites yield a relatively narrow interval of 305 ± 15°C. Stable isotope (O, H, C, S) compositions have been determined in silicate, carbonate, and sulfide minerals. The δ18O and δD values of the mineralizing fluid range from +2.4 to +5.7 and from −43‰ to −20‰, respectively, and are interpreted as having a metamorphic origin. The δ13C values of fluid CO2 are in the range −10.7‰ to −3.9‰, whereas the fluid δ34S is around 0‰. Carbon and sulfur compositions are not diagnostic of their sources, compatible as they are with mantle, magmatic, or average crustal reservoirs. The hydrothermal paragenesis, chlorite–pyrite coexistence, temperature of ore formation, and sulfur isotope evidence indicate relatively reduced fO2 conditions for the mineralizing fluid. Geologic, chemical, and isotopic characteristics of the Cipoeiro deposit are compatible with the class of orogenic gold deposits.  相似文献   

4.
The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ34S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ34S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ34S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ34Spyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe3+ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H2O, not O2. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.  相似文献   

5.
Upper Cretaceous Phosphorites from different localities in Egypt were analyzed for their rare earth elements (REEs) contents and sulfur and strontium isotopes to examine the effect of depositional conditions versus diagenesis on these parameters.The negative Ce and Eu anomalies of the study phosphorites suggest its formation under reducing conditions. However, chondrite-normalized REEs patterns show relative enrichments of LREEs over the HREEs, which is obviously different from the seawater REEs pattern suggesting post-depositional modifications on the REEs distributions during diagenesis. The difference in the REEs concentrations and Ce anomalies among the study localities as well as the similarity between the REEs patterns of these phosphorites and associated black shales might support this interpretation.The concentration of structural SO42− (0.6-3.7%) and their δ34S values (+0.5 to -20‰) in the upper Cretaceous phosphorites in Egypt suggest the formation of these phosphorites in the zone of sulfate reduction. On the other hand, the sulfur isotopes in the pyrite from the study phosphorites (δ34S = +4.6‰ − 23‰ with an average of −7.7‰) are attributed to the influence of seawater from which pyrite was formed during diagenesis. The difference between the δ34S values in the phosphorites (all are positive values) and those in the associated pyrite (mostly negative values) reflect an asymmetric sulfate and sulfide sulfur isotopic composition due to the formation of francolite (source of sulfate) and pyrite (source of sulfide) in different conditions and/or process.The 87Sr/86Sr values of the upper Cretaceous phosphorites in Egypt are very close to the marine values during the Campanian-Maastrichtian time and their average (0.707622) is more or less comparable to the average 87Sr/86Sr values of the Cretaceous-Eocene Tethyan phosphorites. This suggests no post-depositional alteration (i.e. diagenetic effect) on the Sr isotopic composition of these phosphorites.  相似文献   

6.
The role of sulfur in two hydrothermal vent systems, the Logatchev hydrothermal field at 14°45′N/44°58′W and several different vent sites along the southern Mid-Atlantic Ridge (SMAR) between 4°48′S and 9°33′S and between 12°22′W and 13°12′W, is examined by utilizing multiple sulfur isotope and sulfur concentration data. Isotope compositions for sulfide minerals and vent H2S from different SMAR sites range from + 1.5 to + 8.9‰ in δ34S and from + 0.001 to + 0.051‰ in Δ33S. These data indicate mixing of mantle sulfur with sulfur from seawater sulfate. Combined δ34S and Δ33S systematics reveal that vent sulfide from SMAR is characterized by a sulfur contribution from seawater sulfate between 25 and 33%. This higher contribution, compared with EPR sulfide, indicates increased seawater sulfate reduction at MAR, because of a deeper seated magma chamber and longer fluid upflow path length, and points to fundamental differences with respect to subsurface structures and fluid evolution at slow and fast spreading mid-ocean ridges.Additionally, isotope data uncover non-equilibrium isotopic exchange between dissolved sulfide and sulfate in an anhydrite bearing zone below the vent systems at fluid temperatures between 335 and 400 °C. δ34S values between + 0.2 to + 8.8‰ for dissolved and precipitated sulfide from Logatchev point to the same mixing process between mantle sulfur and sulfur from seawater sulfate as at SMAR. δ34S values between ? 24.5 and + 6.5‰ and Δ33S values between + 0.001 and + 0.125‰ for sulfide-bearing sediments and mafic/ultramafic host rocks from drill cores taken in the region of Logatchev indicate a clear contribution of biogenic sulfides formed via bacterial sulfate reduction. Basalts and basaltic glass from SMAR sites with Δ33S = ? 0.008‰ reveal lower Δ33S lower values than suggested on the basis of previously published isotopic measurements of terrestrial materials.We conclude that the combined use of both δ34S and Δ33S provides a more detailed picture of the sulfur cycling in hydrothermal systems at the Mid-Atlantic Ridge and uncovers systematic differences to hydrothermal sites at different mid-ocean ridge sites. Multiple sulfur isotope measurements allow identification of incomplete isotope exchange in addition to isotope mixing as a second important factor influencing the isotopic composition of dissolved sulfide during fluid upflow. Furthermore, based on Δ33S we are able to clearly distinguish biogenic from hydrothermal sulfides in sediments even when δ34S were identical.  相似文献   

7.
《地学前缘(英文版)》2019,10(6):2177-2188
Colloform pyrite with core-rim texture is commonly deposited in carbonate platforms associated with the sulfide ores such as the Caixiashan Pb-Zn deposit.However,the genesis of colloform pyrite in Pb-Zn deposits,its growth controls and their geological implication are insufficiently understood.Integration of in-situ trace element and SIMS sulfur isotopes has revealed geochemical variations among these pyrite layers.These colloform pyrite occur as residual phases of core-rim aggregates,the cores are made up of very fine-grained anhedral pyrite particles,with some rims being made up of fine-grained and poorlycrystallized pyrite,while the other rims were featured with euhedral cubic pyrite.which are cemented by fine-grained calcite and/or dolomite with minor quartz.Sulfur isotope analysis shows that some wellpreserved rims have negative δ~(34)S values(-28.12‰to-0.49‰),whereas most of the cores and rims have positive δ~(34)S values(0 to+44.28‰;peak at+14.91‰).Integrating with the methane and sulfate were observed in previous fluid inclusion study,we suggest that the ~(34)S depleted rims were initially formed by bacteria sulfate reduction(BSR),whereas the positive δ~(34)S values were resulted from the sulfate reduction driven by anaerobic methane oxidation(AOM).The well-developed authigenic pyrite and calcite may also support the reaction of AOM.Combined with petrographic observations,trace element composition of the colloform pyrite reveals the incorporation and precipitation behavior of those high abundance elements in the pyrite:Pb and Zn were present as mineral inclusion and likely precipitated before Fe,as supported by the time-resolved Pb-Zn signal spikes in most of the analyzed pyrite grains.Other metals,such as Hg,Co and Ni,may have migrated as chloride complexes and entered the pyrite lattice.Arsenic and Sb,generally influenced by complex-forming reactions rather than substitution ones,could also enter the pyrite lattice,or slightly predate the precipitation of colloform pyrite as mineral inclusions,which are controlled by their hydrolysis constant in the ore fluids.The colloform pyrite may have grown inward from the rims.The successive BSR reaction process would enrich H_2~(32)S in the overlying water column but reduce the metal content,the nucleation of these pyrite rims was featured by strongly negative sulfur isotopes.The following AOM process should be activated by deformation like the turbidity sediment of the mudstone as the sulfide deposition are associated with fault activities that caused the emission of methane migration upward and simultaneously replenishing the metal in the column.The higher AOM reaction rate and the higher metal supply(not only Fe.but with minor other metals such as Pb and Zn) caused by sediment movement enhanced the metal concentration within the pyrite lattice.  相似文献   

8.
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   

9.
Sulfur mass-independent fractionation (S-MIF) preserved in Archean sedimentary pyrite is interpreted to reflect atmospheric chemistry. Small ranges in Δ33S that expanded into larger fractionations leading up to the Great Oxygenation Event (GOE; 2.45–2.2 Ga) are disproportionately represented by sequences from the Kaapvaal and Pilbara Cratons. These patterns of S-MIF attenuation and enhancement may differ from the timing and magnitude of minor sulfur isotope fractionations reported from other cratons, thus obscuring local for global sulfur cycling dynamics. By expanding the Δ33S record to include the relatively underrepresented São Francisco Craton in Brazil, we suggest that marine biogeochemistry affected S-MIF preservation prior to the GOE. In an early Neoarchean sequence (2763–2730 Ma) from the Rio das Velhas Greenstone Belt, we propose that low δ13Corg (<?30‰) and dampened Δ33S (0.4‰ to ?0.7‰) in banded iron formation reflect the marine diagenetic process of anaerobic methane oxidation. The overlying black shale (TOC up to 7.8%) with higher δ13Corg (?33.4‰ to ?19.2‰) and expanded Δ33S (2.3‰ ± 0.8‰), recorded oxidative sulfur cycling that resulted in enhance preservation of S-MIF input from atmospheric sources of elemental sulfur. The sequence culminates in a metasandstone, where concomitant changes to more uniform δ13Corg (?30‰ to ?25‰), potentially associated with the RuBisCO I enzyme, and near-zero Δ33S (?0.04‰ to 0.38‰) is mainly interpreted as evidence for local oxygen production. When placed in the context of other sequences worldwide, the Rio das Velhas helps differentiate the influences of global atmospheric chemistry and local marine diagenesis in Archean biogeochemical processes. Our data suggest that prokaryotic sulfur, iron, and methane cycles might have an underestimated role in pre-GOE sulfur minor isotope records.  相似文献   

10.
Gold in the Sahinli and Tespih Dere intermediate sulfidation gold-base metal deposits in Western Turkey occurs in relatively deep epithermal quartz veins along with base metal minerals which have epithermal textures, including plumose quartz, vug infills, comb and cockade textures and matrix-supported milled breccias. The total sulfide content of the veins in the area is variable ranging from < 1% to 60% and is dominated by pyrite, galena, sphalerite and chalcopyrite. Sphalerite is Fe-poor (0.6 to 1.4 mol% FeS). Minor amounts of Ag-rich tetrahedrite are present. Primary hydrothermal alteration minerals include illite/muscovite, mixed-layer illite/smectite (11.6 Å) and clinochlore towards the east and, alunite, dickite/nacrite and pyrophyllite towards the west at Sahinli; major illite/muscovite and dickite occur at Tespih Dere and Sarioluk, respectively.Fluid inclusions in main-stage quartz at Sahinli are only liquid-rich, with homogenization temperatures ranging from 220 to 322 °C and the majority of Th values between 250 and 300 °C. Salinity ranges from 4.3 to 6.9 wt.% NaCl equiv. First ice-melting temperatures (Tmf) between ?24.5 and ?19.0 °C indicate that the fluids were dominated by NaCl – H2O during mineralization. The relatively higher average Th at the Tespih Dere deposit (295 °C) is attributed to a relatively deeper level of exposure.Calculated δ18O values indicate that ore-forming hydrothermal fluids in the study area had δ18OH2O ranging from + 1.1 to + 9.7‰ (average = 3.8‰), strongly 18O-enriched compared with present-day hydrothermal meteoric water in the area (δ18O = ?8.5‰). δD values of fluid inclusions in quartz range from ?58 to ?93‰ and δD values of clay minerals and alunite from ?40 to ?119‰. δD values from intermediate argillic alteration (average = ?68‰) in the study area are very similar to δD values of the present-day local geothermal system (average δD = ?54‰) whereas δD values from advanced-argillic alteration (average δD = ?33‰) are very different from the present-day local geothermal system.The δ34S values in samples from the Sahinli and Tespih Dere deposits average ?2.9‰ for pyrite; ?3.3‰ for chalcopyrite; ?5.4‰ for sphalerite and ?7.6‰ for galena. These data are consistent with derivation of the sulfur from either igneous rocks or possibly from local wallrock.  相似文献   

11.
The Tianqiao Pb–Zn deposit in the western Yangtze Block, southwest China, is part of the Sichuan–Yunnan–Guizhou (SYG) Pb–Zn metallogenic province. Ore bodies are hosted in Devonian and Carboniferous carbonate rocks, structurally controlled by a thrust fault and anticline, and carried about 0.38 million tons Pb and Zn metals grading > 15% Pb + Zn. Both massive and disseminated Pb–Zn ores occur either as veinlets or disseminations in dolomitic rocks. They are composed of ore minerals, pyrite, sphalerite and galena, and gangue minerals, calcite and dolomite. δ34S values of sulfide minerals range from + 8.4 to + 14.4‰ and display a decreasing trend from pyrite, sphalerite to galena (δ34Spyrite > δ34Ssphalerite > δ34Sgalena). We interpret that reduced sulfur derived from sedimentary sulfate (gypsum and barite) of the host Devonian to Carboniferous carbonate rocks by thermal–chemical sulfate reduction (TSR). δ13CPDB and δ18OSMOW values of hydrothermal calcite range from –5.3 to –3.4‰ and + 14.9 to + 19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO2 in the hydrothermal fluid was a mixture origin of mantle, marine carbonate rocks and sedimentary organic matter. Sulfide minerals have homogeneous and low radiogenic Pb isotope compositions (206Pb/204Pb = 18.378 to 18.601, 207Pb/204Pb = 15.519 to 15.811 and 208Pb/204Pb = 38.666 to 39.571) that are plotted in the upper crust Pb evolution curve and overlap with that of Devonian to Carboniferous carbonate rocks and Proterozoic basement rocks in the SYG province. Pb isotope compositions suggest derivation of Pb metal from mixed sources. Sulfide minerals have 87Sr/86Sr ratios ranging from 0.7125 to 0.7167, higher than Sinian to Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than basement rocks. Again, Sr isotope compositions are supportive of a mixture origin of Sr. They have an Rb–Sr isotopic age of 191.9 ± 6.9Ma, possibly reflecting the timing of Pb–Zn mineralization. C–O–S–Pb–Sr isotope compositions of the Tianqiao Pb–Zn deposit indicate a mixed origin of ore-forming fluids, which have Pb–Sr isotope homogenized before the mineralization. The Permian flood basalts acted as an impermeable layer for the Pb–Zn mineralization hosted in the Devonian–Carboniferous carbonate rocks.  相似文献   

12.

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.

  相似文献   

13.
The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl2 equiv.). The range of δ34S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ34S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ13CV-PDB from −8.2 to −5.1‰ and δ18OV-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO3− from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.  相似文献   

14.
This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ34SSO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ18OSO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ34SSO4 and δ18OSO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II1) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ34SSO4 and δ18OSO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II2) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ34SSO4 and δ18OSO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II3) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ34SSO4 and δ18OSO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ34SSO4 = 10–35‰ and δ18OSO4 = 7–20‰), soil sulfate (δ34SSO4 = 5.9‰ and δ18OSO4 = 5.8‰) and sewage water (δ34SSO4 = 10.0‰ and δ18OSO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II3), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ34SSO4 and δ18OSO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.  相似文献   

15.
The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD_(H2O-SMOW) and δ~(18)O_(H2O-SMOW) values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H_2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ~(13)C_(PDB) values ranging from-6.2‰ to-4.1‰ and δ~(18)O_(SMOW) values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ~(34)S_(CDT) values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The ~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and ~(208)Pb/~(204)Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates.  相似文献   

16.
The large tonnage Maoling gold deposit (25 t @ 3.2 g/t) is located in the southwest Liaodong Peninsula, North China Craton. The deposit is hosted in the Paleoproterozoic metamorphic rocks. Four stages of mineralization were identified in the deposit: (stage I) quartz-arsenopyrite ± pyrite, (stage II) quartz-gold- arsenopyrite-pyrrhotite, (stage III) quartz-gold- polymetallic sulfide, and (stage IV) quartz-calcite-pyrrhotite. In this paper, we present fluid inclusion, C-H-O-S-Pb-He-Ar isotope data, zircon U-Pb, and gold-bearing sulfide (i.e. arsenopyrite and pyrrhotite) Rb-Sr age of the Maoling gold deposit to constrain its genesis and ore-forming mechanism. Three types of fluid inclusions were distinguished in quartz-bearing veins, including liquid-rich two-phase (WL type), gas-rich two-phase (GL type), and daughter mineral-bearing fluid inclusions (S type). Fluid inclusions data show that the homogenization at temperatures 197 to 372 °C for stage I, 126 to 319 °C for stage II, 119 to 189 °C for stage III, and 115 to 183 °C for stage IV, with corresponding salinities of 3.7 to 22.6 wt.%, 4.7 to 23.2 wt.%, 5.3 to 23.2 wt.%, and 1.7 to 14.9 wt.% NaCl equiv., respectively. Fluid boiling was the critical factor controlling the gold and associated sulfide precipitation at Maoling. Hydrogen and oxygen stable isotopic analyses for quartz yielded δ18O = ?5.0‰ to 9.8‰ and δ D = ?133.5‰ to ?77.0‰. Carbon stable isotopic analyses for calcite and ankerite yielded δ13C = ?2.3‰ to ?1.2‰ and O = 7.9‰ to 14.1‰. The C-H-O isotope data show that the ore-forming fluids were originated from magmatic water with meteoric water input during mineralization. Hydrothermal inclusions in arsenopyrite have 3He/4He ratios of 0.002 Ra to 0.054 Ra, and 40Ar/36Ar rations of 1225 to 3930, indicating that the ore-forming fluids were dominantly derived from crustal sources almost no mantle input. Sulfur isotopic values of Maoling fine-grained granite range from 6.‰1 to 9.8‰, with a mean of 7.7‰, δ34S values of arsenopyrite from the mineralized phyllite (host rock) range from 8.9‰ to 10.6‰, with a mean of 10.0‰, by contrast, δ34S values of sulfides from ore vary between 4.3‰ and 10.6‰, with a mean of 6.8‰, suggesting that sulfur was mainly originated from both the host rock and magma. Lead radioactive isotopic analyses for sulfides yielded 206Pb/204Pb = 15.830–17.103, 207Pb/204Pb = 13.397–15.548, 208Pb/204Pb = 35.478–36.683, and for Maoling fine-grained granite yielded 206Pb/204Pb = 18.757–19.053, 207Pb/204Pb = 15.596–15.612, and 208Pb/204Pb = 38.184–39.309, also suggesting that the ore-forming materials were mainly originated from the host rocks and magma. Zircon U-Pb dating demonstrates that the Maoling fine-grained granite was emplaced at 192.7 ± 1.8 Ma, and the host rock (mineralized phyllite) was emplaced at some time after 2065.0 ± 27.0 Ma. Arsenopyrite and pyrrhotite give Rb–Sr isochron age of 188.7 ± 4.5 Ma, indicating that both magmatism and mineralization occurred during the Early Jurassic. Geochronological and geochemical data, together with the regional geological history, indicate that Early Jurassic magmatism and mineralization of the Maoling gold deposit occurred during the subducting Paleo-Pacific Plate beneath Eurasia, and the Maoling gold deposit is of the intrusion-related gold deposit type.  相似文献   

17.
The Song Hien rift basin is considered to be one of the most important regions of gold mineralisation in North East Vietnam. A number of gold deposits in the Song Hien rift basin are hosted in Triassic and Devonian sedimentary formations of the basin. The largest among them are the Bo Va, Tham Riem and Khung Khoang deposits. The Bo Va deposit is hosted in carbonaceous sedimentary rocks of Triassic age, whereas the Tham Riem and Khung Khoang deposits are hosted in carbonaceous sedimentary rocks of Devonian ages. Based on the mineral composition of the ores, the deposits can be divided into to two types: (i) pyrite dominated and (ii) pyrite-arsenopyrite dominated. The Khung Khoang is of the first type and the Bo Va and Tham Riem deposits belong to the second type. The isotopic composition of pyrite and arsenopyrite in the Tham Riem deposit however, is close to that for the ores of the Bo Va deposit. The δ34S value for pyrite ranging from −3.7‰ to −7.4‰ and for arsenopyrite ranging from −3.2‰ to 7.4‰. The δ34S of pyrite in the ore from the Khung Khoang deposit however, has a much heavier isotopic composition of +18.9 to +20.2‰. A narrow range of the variation of sulfur isotopic composition of pyrite and arsenopyrite, the presence of visible gold as inclusions, the presence of chalcopyrite, sphalerite and other inclusions in arsenopyrite and pyrite, the large size of the grains of major ore minerals allow us to assume that the primary gold ores of the Bo Va and Tham Riem deposits underwent metamorphic transformations. The absence of arsenic, antimony, mercury and other characteristic elements in the ores of the Khung Khoang deposit, and substantially heavier isotopic composition of sulfur similar to the sulfur isotopic composition of marine sulfates in the Devonian, allow us to assume another source of the ore components, not connected with the Triassic sedimentary rocks of the Song Hien rift.  相似文献   

18.
Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ34S 0.0 to 9.6‰, avg. δ34S 4.7‰; n = 60), being close to the associated igneous rocks (~ 0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (< 36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ34S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (206Pb/204Pb 17.541 ± 0.004 to 19.268 ± 0.001, 207Pb/204Pb 15.451 ± 0.001 to 15.684 ± 0.001, 208Pb/204Pb 37.557 ± 0.008 to 38.988 ± 0.002, n = 21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ34S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing.  相似文献   

19.
《Resource Geology》2018,68(3):275-286
The volcanic‐hosted Xiangshan uranium orefield is the largest uranium deposit in South China. Recent exploration has discovered extensive Pb–Zn mineralization beneath the uranium orebodies. Detailed geological investigation reveals that the major metallic minerals include pyrite, sphalerite, galena, and chalcopyrite, whilst the major non‐metallic minerals include quartz, sericite, and calcite. New δ18Ofluid and δDfluid data indicate that the ore‐forming fluids were mainly derived from magmatic, and the sulfide δ34S values (2.2–6.9‰) suggest a dominantly magmatic sulfur source. The Pb isotope compositions are homogeneous (206Pb/204Pb = 18.120–18.233, 207Pb/204Pb = 15.575–15.698, and 208Pb/204Pb = 37.047–38.446). The 87Sr/86Sr ratios of sulfide minerals range from 0.7197 to 0.7204, which is much higher than volcanic rocks and fall into the range of metamorphic basement. Lead and strontium isotopic compositions indicate that the metallogenic materials probably were derived from metamorphic basement. Pyrite Rb–Sr dating of the ores yielded 131.3 ± 4.0 Ma, indicating that the Pb–Zn mineralization occurred in the Early Cretaceous.  相似文献   

20.
Two epithermal gold deposits (Kartaldağ and Madendağ) located in NW Turkey have been characterized through the detailed examinations involving geologic, mineralogical, fluid inclusion, stable isotope, whole-rock geochemistry, and geochronology data.The Kartaldağ deposit (0.01–17.65 ppm Au), hosted by Eocene dacite porphyry, is associated with four main alteration types with characteristic assemblage of: i) chlorite/smectite–illite ± kaolinite, ii) quartz–kaolinite, iii) quartz–alunite–pyrophyllite, iv) quartz–pyrite, the last being characterized by three distinct quartz generations comprising massive/vuggy (early), fine–medium grained, vug-lining (early), and banded, colloform, comb (late) textures. Observed sulfide minerals are pyrite, covellite, and sphalerite. Oxygen and sulfur isotope analyses, performed on quartz (δ18O(quartz): 7.93 to 8.95‰ and calculated δ18O(H2O): − 7.95 to 1.49‰) and pyrite (δ34S(pyrite): − 4.8‰ and calculated δ34S(H2S): − 6.08 to − 7.20‰) separates, suggest a meteoric water source for water in the hydrothermal fluid, and an igneous source for the sulfur dissolved in ore-related fluids. Microthermometric analyses of primary fluid inclusion assemblages performed on quartz (late quartz generation) yield temperatures (Th) dominantly in the range of 245–285 °C, and generally low salinity values at 0 to 1.7 wt.% NaCl eq. Based on the quartz textures and the associated base metal concentrations, along with fluid inclusion petrography, the early vug-lining quartz is considered to have been associated with the mineralization possibly through a boiling and a late mixing process at > 285 °C.The Madendağ deposit (0.27–20.60 ppm Au), hosted by Paleozoic mica schists, is associated with two main alteration types: sericite–illite–kaolinite, and quartz–pyrite dominated by two distinct quartz generations i) early colloform, comb and banded quartz and ii) late quartz, forming the cement in hydrothermal breccia. Whereas oxygen isotope analyses of quartz (δ18O(quartz): 9.55 to 18.19‰ and calculated δ18O(H2O): − 2.97 to 5.54‰) suggest varying proportions of meteoric and magmatic sources for the ore bearing fluid, sulfur isotope ratios (δ34S(pyrite): − 2.2‰ and calculated δ34S(H2S): (− 3.63) to (− 3.75) ‰) point to an essentially magmatic source for sulfur with or without contribution from sedimentary sources. Microthermometric analysis carried out on primary fluid inclusion populations of a brecciated sample (early quartz), give a temperature (Th) range of 235–255 °C and 0.0 to 0.7 wt.% NaCl eq. salinity. Based on the textural relationship, base metal and high gold contents, the ore precipitation stage is associated with late stage quartz formation via a possible boiling process.The presence of alunite, pyrophyllite and kaolinite, vuggy quartz and covellite suggest a high-sulfidation type of epithermal deposit for Kartaldağ. On the other hand, Madendağ is identified as an adularia-sericite type owing to the presence of significant sericite, neutral pH clays (mostly illite, chlorite/smectite, and kaolinite), low temperature quartz textures (e.g., colloform, comb, and banded quartz), and limited sulfide minerals.Given the geographical proximity of Kartaldağ and Madendağ deposits, the similar temperature and salinity ranges obtained from their fluid inclusions, and the similar ages of igneous rocks in both deposits (Kartaldağ: 40.80 ± 0.36 to 42.19 ± 0.45 Ma, Madendağ: 43.34 ± 0.85 Ma) the mineralizing systems in both deposits are considered to be genetically related.  相似文献   

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