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1.
The Silesia–Cracow district in Poland has been one of the world’s principal sources of zinc from nonsulfide zinc ore (Polish: galman). The still remaining nonsulfide ore resources can be estimated at 57 Mt at 5.6% Zn and 1.4% Pb. Nonsulfide mineralization is mainly hosted by Lower Muschelkalk (Triassic) limestone and is associated with different generations of the hydrothermal ore-bearing dolomite (OBD I, II, III). A fundamental ore control is believed to have been exerted by the basement faults, which were repeatedly reactivated during the Alpine tectonic cycle, leading to the formation of horst-and-graben structures: these dislocations may have caused short periods of emersion and the circulation of meteoric waters during the Cenozoic. Nonsulfide ores show a wide range of morphological characteristics and textures. They occur as earthy masses, crystalline aggregates, and concretions in cavities. Breccia and replacement textures are also very common. The most important mineral phases are: smithsonite, Fe–smithsonite, Zn–dolomite, goethite, and Fe–Mn(hydr)oxides. Minor hemimorphite and hydrozincite have also been detected. Two distinct nonsulfide ore types occur: the predominant red galman and the rare white galman. In the white galman, Fe–smithsonite and Zn–dolomite are particularly abundant. This ore type is commonly considered as a peripheral hydrothermal alteration product related to the same fluids that precipitated both the OBD II–III and the sulfides. In contrast, a supergene origin is commonly assumed for the red galman. Evidence of the petrographic and mineralogical difference between white and red galman is also found in stable isotope data. Smithsonite from red galman shows a limited range of δ 13CVPDB values (−10.1 to −11.4‰), and δ 18OVSMOW values (25.3‰ to 28.5‰, mean 26.8 ± 0.3‰). The uniform and low carbon isotope values of red galman smithsonite are unusual for supergene carbonate-hosted deposits and indicate the predominance of a single organic carbon source. Smithsonite from white galman has a more variable, slightly more positive carbon isotope (−2.9‰ to −7.4‰), but broadly similar oxygen isotope composition (26.8‰ to 28.9‰). The relationship of the white galman ore with the hydrothermal system responsible for OBD II and sulfide generation is still uncertain. The most important paleoweathering events took place in both Lower and Upper Silesia during Late Cretaceous up to Paleogene and early Neogene time. During this period, several short-lasting emersions and intense weathering episodes facilitated the formation of sinkholes in the Triassic carbonate rocks and the oxidation of sulfide orebodies through percolating meteoric waters. These phenomena may have lasted until the Middle Miocene.  相似文献   

2.
The Jabali Zn–Pb–Ag deposit is located about 110 km east of Sana'a, the capital of Yemen, along the western border of the Marib-Al-Jawf/Sab'atayn basin. The economic mineralization at Jabali is a nonsulfide deposit, consisting of 8.7 million tons at an average grade of 9.2% zinc, derived from the oxidation of primary sulfides. The rock hosting both primary and secondary ores is a strongly dolomitized carbonate platform limestone of the Jurassic Shuqra Formation (Amran Group). The primary sulfides consist of sphalerite, galena and pyrite/marcasite. Smithsonite is the most abundant economic mineral in the secondary deposit, and is associated with minor hydrozincite, hemimorphite, acanthite and greenockite. Smithsonite occurs as two main generations: smithsonite 1, which replaces both host dolomite and sphalerite, and smithsonite 2, occurring as concretions and vein fillings in the host rock. At the boundary between smithsonite 1 and host dolomite, the latter is widely replaced by broad, irregular bands of Zn-bearing dolomite, where Zn has substituted for Mg. The secondary mineralization evolved through different stages: 1) alteration of original sulfides (sphalerite, pyrite and galena), and release of metals in acid solutions; 2) alteration of dolomite host rock and formation of Zn-bearing dolomite; 3) partial dissolution of dolomite by metal-carrying acid fluids and replacement of dolomite and Zn-bearing dolomite by a first smithsonite phase (smithsonite 1). To this stage also belong the direct replacement of sphalerite and galena by secondary minerals (smithsonite and cerussite); 4) precipitation of a later smithsonite phase (smithsonite 2) in veins and cavities, together with Ag- and Cd-sulfides.The δ18O composition of Jabali smithsonite is generally lower than in other known supergene smithsonites, whereas the carbon isotope composition is in the same range of the negative δ13C values recorded in most supergene nonsulfide ores. Considering that the groundwaters and paleo-groundwaters in this area of Yemen have negative δ18O values, it can be assumed that the Jabali smithsonite precipitated in different stages from a combination of fluids, possibly consisting of local groundwaters variably mixed with low-temperature hydrothermal waters. The carbon isotope composition is interpreted as a result of mixing between carbon from host rock carbonates and soil/atmospheric CO2.The most favorable setting for the development of the Jabali secondary deposit could be placed in the early Miocene (~ 17 Ma), when supergene weathering was favored by major uplift and exhumation resulting from the main phase of Red Sea extension. Low-temperature hydrothermal fluids may have also circulated at the same time, through the magmatically-induced geothermal activity in the area.  相似文献   

3.
The Hakkari nonsulfide zinc deposit is situated close to the southeastern border of Turkey. Here both sulfide and nonsulfide Zn ≫ Pb ores are hosted in carbonate rocks of the Jurassic Cudi Group with features typical of carbonate-hosted supergene nonsulfide zinc mineralization. The regional strike extent of the mineralized district is at least 60 km. The age of the supergene deposit has not been determined, but it is probable that the main weathering happened during Upper Tertiary, possibly between Upper Miocene and Lower Pliocene. The Hakkari mineralization can be compared to other carbonate-hosted Zn–Pb deposits in Turkey, and an interpretation made of its geological setting. The zinc mineral association at Hakkari typically comprises smithsonite and hemimorphite, which apparently replace both sulfide minerals and carbonate host rock. Two generations of smithsonite are present: the first is relatively massive, the second occurs as concretions in cavities as a final filling of remnant porosity. Some zinc is also hosted within Fe–Mn-(hydr)oxides. Lead is present in cerussite, but also as partially oxidized galena. Lead can also occur in Mn-(hydr)oxides (max 30% PbO). The features of the supergene mineralization suggest that the Hakkari deposit belongs both to the “direct replacement” and the “wall-rock replacement” types of nonsulfide ores. Mineralization varies in style from tabular bodies of variable thickness (< 0.5 to 13 m) to cross-cutting breccia zones and disseminated ore minerals in pore spaces and fracture planes. At Hakkari a As–Sb–Tl(≫ Hg) geochemical association has been detected, which may point to primary sulfide mineralization, quite different from typical MVT.  相似文献   

4.
“Nonsulfides” is a term, which comprises a series of oxidized Zn(Pb)-ore minerals. It has also been used to define a special deposit type, mainly considered as derived from the weathering of Zn(Pb) sulfide concentrations. However, nonsulfide zinc deposits have been distinguished between supergene and hypogene, according to their mineralogy, geological characteristics and genetic setting. The supergene deposits formed by weathering and oxidation at ambient temperatures, whereas the hypogene ones are considered hydrothermal, or associated with metamorphic processes on primary sulfide ores.In this review paper, a comparison between a number of several nonsulfide deposits has been carried out: typical “Calamines”, peculiar “Calamines” and “Others”. The whole group comprises deposits of typical supergene origin, mixed supergene–hypogene mineralizations, and oxidized concentrations characterized by different metals only locally associated with zinc. The Zn–Pb nonsulfide concentrations hosted in carbonate rocks, which are mainly attributed to “wall-rock replacement” and “direct-replacement” supergene processes, are the typical “Calamines” (Liège district, Belgium; Iglesias district, Italy; Silesia–Cracow district, Poland). Peculiar “Calamine” deposits are those mineralizations that have been generally considered as supergene, but which are instead genetically related, at least partly, to hypogene processes (e.g. Angouran, Iran; Jabali, Yemen), though mineralogically and texturally similar to supergene nonsulfide deposits. The “Others” are prevailingly supergene nonsulfide zinc deposits not hosted in carbonate rocks (Skorpion, Namibia; Yanque, Peru), or characterized by other metals as main commodities, like lead (Magellan, Australia), silver (Sierra Mojada, Mexico; Wonawinta, Australia) or vanadium (Otavi Mountainland, Namibia).Minerals of current economic importance in most “Calamine” deposits are smithsonite, hydrozincite, and cerussite. This mineralogical association is generally simple but, when the “Calamines” are dolomite-hosted, one of the consequences of the “wall-rock replacement” process is the generation of a series of economically useless Zn- and Mg-bearing mixed carbonate phases. Secondary deposits hosted in silicatic (sedimentary or volcanic) rocks mainly contain hemimorphite and/or sauconite. Lead-, Ag- and V-rich nonsulfide ores are characterized by a more complex mineralogical association: mixed Pb-carbonates, Pb-sulfates, Pb-phosphates, Pb-arsenates, various Ag-sulfosalts, and Zn–Pb–Cu-vanadates.Carbon and oxygen stable isotope studies allow distinguishing between supergene and hypogene nonsulfide deposits, evaluating the effects of oxidative heating and even gaining indirect paleoclimatic information. The oxygen-isotope variation of the individual carbonate minerals within a deposit is relatively small, indicating constant formation temperatures and a single, meteoric fluid source. Carbon-isotope values are highly variable, thus suggesting several isotopically distinct carbon sources.Periods of paleoclimatic switch-overs from seasonally humid/arid to hyperarid have been considered as the most favorable conditions for the formation and preservation of supergene nonsulfide deposits. However, while several recent nonsulfide deposits throughout the world are positioned between 15° and 45° N latitude, thus pointing to a warm and humid weathering climate, others have been deposited in sub-Arctic regions.The economic value of the nonsulfide Zn(Pb–Ag–V) ores is highly variable, because more than in the case of metallic sulfide deposits, it resides not only on the geological setting, but also on their mineralogy that can directly influence processing and metallurgy.  相似文献   

5.
The unusually high grade hypogene zinc ore at Angouran in northwestern Iran (40.4% Zn, 1.9% Pb in the sulfide ore, 28.1% Zn, 4.4% Pb in the carbonate ore, and 110 g/t Ag) formed from an initially highly saline, reduced, relatively acid hydrothermal brine at two successive sulfide and carbonate ore stages. The early ore stage consists of multiple phases of sphalerite dominated sulfide ore breccia with subordinate amounts of galena (± Pb sulfosalts), minor pyrite, and abundant barite. Sphalerite precipitated at moderate temperatures (≥ 155 °C) because of pH increase in the presence of hangingwall marble. Smithsonite precipitated at a higher pH value (≥ 7) and at lower temperatures (≤ 120 °C) from dilute solutions (salinities close to zero) by mixing of the Zn bearing brines with cool, HCO3− bearing waters. The first melting points of the primary (LV) fluid inclusions in sphalerite and in hydrothermal quartz are unusually low (≤ − 60 °C), close to the eutectic point of the ZnCl2–H2O system (− 62 °C). Total salinities taken from the ZnCl2–H2O system as a best approximation correspond to 26–41 eq mass % ZnCl2. The initial brine evolved to a CaCl2–NaCl rich solution with 27 eq mass % salinity. Gas densities (≤ 0.1 g cm− 3 for water vapor and ≤ 0.18 g cm− 3 for CO2) in the fluid inclusions indicate low pressure (≤ 5 bar for water vapor, and ≤ 100 bar for CO2) at the entrapment temperatures.At the first carbonate ore stage sulfides continued to precipitate characteristically as arsenopyrite with minor amounts of galena and pyrite. The abrupt change of the fluid composition at the sulfide–carbonate boundary was accompanied by a change of the fluid temperature and pressure that produced brecciation of the sulfide ore matrix and an almost total dissolution of barite and replacement by the hypogene smithsonite. Alteration is restricted to ore deposition and consists of weak sericitization and silicification with local dolomitization at the sulfide ore stage, and pervasive dissolution of the hangingwall marble, in particular at the carbonate ore stage.The breccia orebody at Angouran is sited at the crestal portion of a domed antiform at the lithological and thrust boundary of Neoproterozoic–Lower Cambrian footwall schists and the hangingwall marble in rapidly uplifted and exhumated Angouran Block east of the Geynardjeh Thrust Fault. The footwall schists occupy a detachment fault zone above imbricated nappe sheets of the basement metamorphic complex of the Sanandaj–Sirjan zone. During the Pliocene, the nappe sheets were thrust toward the southwest onto the Miocene felsic volcanic rocks of the Urumieh Dokhtar Volcanic Belt that are intruded by 10 Ma late Miocene basalts. The 11.9 Ma and 18.4 Ma zircon ages of the felsic volcanic rocks indicate the lower age limit of the ore body emplacement.The associations with large scale, mid-late Miocene, felsic volcanism along the active Tethyan belt, as well as the ubiquitous presence of the volcanic rock clasts in the sphalerite ore matrix, provide strong evidence of the involvement of hydrothermal processes at Angouran. Ore fluids were successively and pulsatorily generated within the seismically active region. A following geothermal activity appears to have had a significant input in the formation of the carbonate ore of the hypogene, as well as the supergene stage. Stable isotope data suggest complex interaction of element sources and processes. Allowing a broad interpretation, the sulfur isotopic composition of the sulfides δ34S (3.9 to 7.4‰) suggests that the sulfur could be sourced from evolving, mixed magmatic–basinal brine. The isotopic composition of the hypogene smithsonites (δ13C: 2.72 to 5.51‰, δ18O: 18.4 to 22.8‰) broadly supports the local geology and field relationships, which comply with a marble wallrock source for the carbonate ores. They lend support to the assumption that smithsonite was deposited from solutions with isotopic composition similar to those involved in the hydrothermal dolomitization of the marbles. The excess of dissolved marble precipitated as large volumes of travertine and as late calcite veins (δ13C: 18.8 to 20.3‰, δ18O: 3.1 to 6.4‰) at the mineralization site. Isotope values of the travertine (δ13C: 4.5 to 6.6‰, δ18O: 20.1 to 21.1‰ V-SMOW) are consistent with the involvement of CO2 derived from thermogenic decarbonization of the host marble by waters of dominantly meteoric origin, most likely concomitantly with ore forming processes.The Angouran deposit is the only reported case of a two stage, hypogene zinc sulfide–zinc carbonate mineralization, and represents a new style of nonsulfide zinc mineralization.  相似文献   

6.
The Dongsheng sandstone-type uranium deposit is one of the large-sized sandstone-type uranium deposits discovered in the northern part of the Ordos Basin of China in recent years. Geochemical characteristics of the Dongsheng uranium deposit are significantly different from those of the typical interlayered oxidized sandstone-type uranium ore deposits in the region of Middle Asia. Fluid inclusion studies of the uranium deposit showed that the uranium ore-forming temperatures are within the range of 150–160℃. Their 3He/4He ratios are within the range of 0.02–1.00 R/Ra, about 5–40 times those of the crust. Their 40Ar/36Ar ratios vary from 584 to 1243, much higher than the values of atmospheric argon. The δ18OH2O and δD values of fluid inclusions from the uranium deposit are -3.0‰– -8.75‰ and -55.8‰– -71.3‰, respectively, reflecting the characteristics of mixed fluid of meteoric water and magmatic water. The δ18OH2O and δD values of kaolinite layer at the bottom of the uranium ore deposit are 6.1‰ and -77‰, respectively, showing the characteristics of magmatic water. The δ13CV-PDB and δ18OH2O values of calcite veins in uranium ores are -8.0‰ and 5.76‰, respectively, showing the characteristics of mantle source. Geochemical characteristics of fluid inclusions indicated that the ore-formation fluid for the Dongsheng uranium deposit was a mixed fluid of meteoric water and deep-source fluid from the crust. It was proposed that the Jurassic-Cretaceous U-rich metamorphic rocks and granites widespread in the northern uplift area of the Ordos Basin had been weathered and denudated and the ore-forming elements, mainly uranium, were transported by meteoric waters to the Dongsheng region, where uranium ores were formed. Tectonothermal events and magmatic activities in the Ordos Basin during the Mesozoic made fluids in the deep interior and oil/gas at shallow levels upwarp along the fault zone and activated fractures, filling into U-bearing clastic sandstones, thus providing necessary energy for the formation of uranium ores.  相似文献   

7.
The Janggun iron deposits, Republic of␣Korea, occur as lens-shaped magnesian skarn, magnetite and base-metal sulfide orebodies developed in the Cambrian Janggun Limestone Formation. Mineralization stage of the deposits can be divided into two separate events. The skarn stage (107 Ma) consists of magnetite, pyrrhotite, base-metal sulfides, carbonates and magnesian skarn minerals. The hydrothermal stage (70 Ma) consists of base-metal sulfides, native bismuth, bismuthinite, tetrahedrite, boulangerite, bournonite and stannite. Mineral assemblages, chemical compositions and thermodynamic considerations indicate that formation temperatures, −log fs2 and −log fo2 values of ore fluids from the skarn stage were 433 to 345 °C, 8.1 to 9.7 bar and 29.4 to 31.6 bar, and the hydrothermal stage was 245 to 315 °C, 10.4 to 13.2 bar and 33.6 to 35.4 bar, respectively. Thermochemical considerations indicate that the XCO2 during magnesian skarnization ranged from 0.06 to 0.09, and the activity of H+ presumably decreased when the fluids equilibrated with host dolomitic limestone which resulted in a pH change from about 6.1 to 7.8, and decreases in fo2 and fs2. The δ34S values of ore sulfides have a wide range from 3.2 to 11.6 ‰ (CDT). Calculated 34SH2 S values of ore fluids are 2.9 to 5.4 ‰ (skarn stage) and 8.7 to 13.5 ‰ (hydrothermal stage). These are interpreted to represent an initial deep-seated, igneous source of sulfur which gave way to influence of oxidized sedimentary sulfur to hydrothermal stage. The δ13C values of carbonates in ores range from −4.6 to −2.5 ‰ (PDB). It is likely that carbon in the ore fluids was a mixture of deep-seated magmatic carbon and dissolved carbon of dolomitic limestone. The δ18OH2 O and δD values (SMOW) of water in the ore fluids were 14.7 to 1.8 and −85 to −73 ‰ during the skarn stage and 11.1 to −0.2 and −87 to −80 ‰ in the hydrothermal stage. Received: 5 March 1997 / Accepted: 28 August 1997  相似文献   

8.
The Spessart district (SW Germany), located at the southwestern margin of the Permian Kupferschiefer basin in Central Europe, hosts abundant stratabound and structurally controlled base metal mineralization. The mineralization styles identified are (1) stratabound Cu-Pb-Zn-(Ag) ores in Zechstein sedimentary rocks, (2) structurally controlled Cu-As-(Ag) ores in Zechstein sedimentary rocks, (3) crosscutting Co-Ni-(Bi)-As and Cu-Fe-As veins, (4) stratabound metasomatic Fe-Mn carbonate ores in Zechstein dolomite, (5) barren barite veins, and (6) Fe-Mn-As veins in Permian rhyolites. Building on previous work that involved mineralogical, textural, and chemical characterization of the major mineralization types, we have performed a comprehensive sulfur isotope study that applied both conventional and novel laser-ablation multi-collector inductively coupled plasma mass spectrometry techniques. The δ34S values of sulfide minerals from the different ore types are consistently negative and highly variable, in the range between −44.5‰ and −3.9‰, whereas the δ34S values of barite are all positive in the range between 4.7‰ and 18.9‰. Remarkably, stratabound and structurally controlled mineralization in Zechstein sedimentary rocks has the least negative δ34S values, whereas vein-type deposits have consistently more negative δ34S values. The observed pattern of sulfide δ34S values can be best interpreted in terms of fluid mixing at the basement-cover interface. Hydrothermal fluids originating from the crystalline basement migrated upward along subvertical fault zones and were periodically injected into groundwaters that were flowing in the post-Variscan sedimentary cover. These groundwaters had interacted with the Zechstein sedimentary rocks, resulting in fluids characterized by elevated concentrations of reduced sulfur (with negative δ34S values) and alkaline pH. Repeated mixing between both chemically contrasting fluids caused rapid and efficient precipitation of sulfide ore minerals in hydrothermal veins with highly variable but distinctly negative δ34S values.  相似文献   

9.
Summary The Dachang Sn-polymetallic ore district is one of the largest tin producing districts in China. Its origin has long been in dispute between magmatic-hydrothermal replacement and submarine exhalative-hydrothermal origin. The Dachang ore district comprises several types of ore deposits, including the Lamo magmatogenic skarn deposit near a granite intrusion, the Changpo-Tongkeng bedded and vein-type sulfide deposit, and the Gaofeng massive sulfide deposit. Sulfide minerals from the Lamo skarn ores show δ34S values in the range between −3 and +4‰ with a mean close to zero, suggesting a major magmatic sulfur source that likely was the intrusive Longxianggai granite. Sulfide minerals from the Gaofeng massive ores show higher δ34S values between +5 and +12‰, whereas sulfide minerals from the Changpo-Tongkeng bedded ores display lighter δ34S values between −7 and −0.2‰. The difference in the sulfur isotope ranges in the two deposits can be interpreted by different degrees of inorganic thermochemcial reduction of marine sulfate using a one-step batch separation fractionation model. Sulfur isotopic compositions from the vein-type ores at Changpo-Tongkeng vary widely from −8 to +4‰, but most of the data cluster around −2.9‰, which is close to that of bedded ores (−3.6‰). The sulfur in vein-type ores might be derived from bedded ores or it represents a mixture of magmatic- and sedimentary-derived sulfur. Pb isotopic compositions of sulfide minerals in the Dachang ore district reveal a difference between massive and bedded ores, with the massive ores displaying more radiogenic Pb isotope ratios. Correlations of 206Pb/204Pb and 207Pb/204Pb or 208Pb/204Pb for the massive and bedded ores are interpreted as two-component mixing of Pb leached from sedimentary host rocks and from deep-seated Precambrian basement rocks composed of metamorphosed volcano-sedimentary rocks. Pb isotopic compositions of sulfide minerals from vein-type ores overlap with those of bedded sulfides. Similar to the sulfur, the lead in vein-type ores might be derived from bedded ores. Skarn ores at Lamo show very limited variations in Pb isotopic compositions, which may reflect a major magmatic-hydrothermal lead source. Helium isotope data of fluid inclusions trapped in sulfides indicate that He in the massive and bedded ores has a different origin than He in fluorite of granite-related veins. The 3He/4He ratios of 1.2–2.9 Ra of fluid inclusions from sulfides at Gaofeng and Changpo-Tongkeng imply a contribution of mantle-derived fluids. Overall our data support a submarine exhalative-hydrothermal origin for the massive and bedded ore types at Dachang. Supplementary material to this paper is available in electronic form at Appendix available as electronic supplementary material  相似文献   

10.
Vein-type tin mineralization in the Dadoushan deposit, Laochang ore field, Gejiu district, SW China, is predominantly hosted in Triassic carbonate rocks (Gejiu Formation) over cupolas of the unexposed Laochang equigranular granite intrusion. The most common vein mineral is tourmaline, accompanied by skarn minerals (garnet, diopside, epidote, phlogopite) and beryl. The main ore mineral is cassiterite, accompanied by minor chalcopyrite, pyrrhotite, and pyrite, as well as scheelite. The tin ore grade varies with depth, with the highest grades (~1.2 % Sn) prevalent in the lower part of the vein zone. Muscovite 40Ar–39Ar dating yielded a plateau age of 82.7 ± 0.7 Ma which defines the age of the vein-type mineralization. Measured sulfur isotope compositions (δ 34S = −4.1 to 3.9 ‰) of the sulfides (arsenopyrite, chalcopyrite, pyrite, and pyrrhotite) indicate that the sulfur in veins is mainly derived from a magmatic source. The sulfur isotope values of the ores are consistent with those from the underlying granite (Laochang equigranular granite, −3.7 to 0.1 ‰) but are different from the carbonate wall rocks of the Gejiu Formation (7.1 to 11.1 ‰). The calculated and measured oxygen and hydrogen isotope compositions of the ore-forming fluids (δ 18OH2O = −2.4 to 5.5 ‰, δD = −86 to −77 ‰) suggest an initially magmatic fluid which gradually evolved towards meteoric water during tin mineralization.  相似文献   

11.
The Mississippi Valley-type (MVT) Pb–Zn ore district at Mežica is hosted by Middle to Upper Triassic platform carbonate rocks in the Northern Karavanke/Drau Range geotectonic units of the Eastern Alps, northeastern Slovenia. The mineralization at Mežica covers an area of 64 km2 with more than 350 orebodies and numerous galena and sphalerite occurrences, which formed epigenetically, both conformable and discordant to bedding. While knowledge on the style of mineralization has grown considerably, the origin of discordant mineralization is still debated. Sulfur stable isotope analyses of 149 sulfide samples from the different types of orebodies provide new insights on the genesis of these mineralizations and their relationship. Over the whole mining district, sphalerite and galena have δ 34 S values in the range of –24.7 to –1.5‰ VCDT (–13.5 ± 5.0‰) and –24.7 to –1.4‰ (–10.7 ± 5.9‰), respectively. These values are in the range of the main MVT deposits of the Drau Range. All sulfide δ 34 S values are negative within a broad range, with δ 34 S pyrite <δ 34 S sphalerite <δ 34 S galena for both conformable and discordant orebodies, indicating isotopically heterogeneous H2S in the ore-forming fluids and precipitation of the sulfides at thermodynamic disequilibrium. This clearly supports that the main sulfide sulfur originates from bacterially mediated reduction (BSR) of Middle to Upper Triassic seawater sulfate or evaporite sulfate. Thermochemical sulfate reduction (TSR) by organic compounds contributed a minor amount of 34S-enriched H2S to the ore fluid. The variations of δ 34 S values of galena and coarse-grained sphalerite at orefield scale are generally larger than the differences observed in single hand specimens. The progressively more negative δ 34 S values with time along the different sphalerite generations are consistent with mixing of different H2S sources, with a decreasing contribution of H2S from regional TSR, and an increase from a local H2S reservoir produced by BSR (i.e., sedimentary biogenic pyrite, organo-sulfur compounds). Galena in discordant ore (–11.9 to –1.7‰; –7.0 ± 2.7‰, n = 12) tends to be depleted in 34 S compared with conformable ore (–24.7 to –2.8‰, –11.7 ± 6.2‰, n = 39). A similar trend is observed from fine-crystalline sphalerite I to coarse open-space filling sphalerite II. Some variation of the sulfide δ 34 S values is attributed to the inherent variability of bacterial sulfate reduction, including metabolic recycling in a locally partially closed system and contribution of H2S from hydrolysis of biogenic pyrite and thermal cracking of organo-sulfur compounds. The results suggest that the conformable orebodies originated by mixing of hydrothermal saline metal-rich fluid with H2S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralization.  相似文献   

12.
The relation of two well-known ancient carbonate deposits to hydrocarbon seepage was confirmed by this study. Archaea are found to be associated with the formation of Oxfordian seep carbonates from Beauvoisin and with a Miocene limestone from Marmorito ("tube-worm limestone"). Carbonates formed due to a mediation by archaea exhibit extremely positive or extremely negative δ13Ccarbonate values, respectively. Highly positive values (+15‰) reflect the use of 13C-enriched CO2 produced by methanogenesis. Low δ13C values of the Marmorito carbonates (–30‰) indicate the oxidation of seepage-derived hydrocarbons. Likewise, the δ13C content of specific tail-to-tail linked isoprenoids, biomarkers for archaea, was found to be strikingly depleted in these samples (as low as –115‰). The isotopic signatures corroborate that archaea were involved in the cycling of seepage-derived organic carbon at the ancient localities. Another Miocene limestone ("Marmorito limestone") shows a strong imprint of methanotrophic bacteria as indicated by δ13C values of carbonate as low as –40‰ and biomarker evidence. Epifluorescence microscopy and field-emission scanning electron microscopy revealed that bacterial biofilms were involved in carbonate aggregation. In addition to lucinid bivalves previously reported from both localities, we infer that sponges from Beauvoisin and tube worms from Marmorito depended on chemosynthesis as well. Low δ13C values of nodules related to sponge taphonomy (–27‰) indicate that sponges might have been linked to an enhanced hydrocarbon oxidation. Tube worm fossils from Marmorito closely resemble chemosynthetic pogonophoran tube worms from Recent cold seeps and are embedded in isotopically light carbonate (δ13C –30‰). Received: 13 October 1998 / Accepted: 5 February 1999  相似文献   

13.
Two Mississippi Valley-type (MVT) ore deposits, Kicking Horse and Monarch, have been studied with the aim of comparing the ores at the two localities and to characterize the origin of the mineralizing fluids and the ore formation process(es). Both deposits are hosted by the Middle Cambrian Cathedral Formation carbonate host rocks, Kicking Horse on the north and Monarch on the south flank of the Kicking Horse valley near Field (SE British Columbia). The ore bodies are situated at the transition of (western) basinal to (eastern) shallow-water strata of the paleo-Pacific passive margin succession in the Cordilleran Foreland Province of the Western Canada Sedimentary Basin. Both deposits are related spatially to normal faults. In both localities, the ore minerals are dominated by pyrite, sphalerite, and galena. Dolomite, minor quartz, and calcite are also present in close association with the ores. The salinity (21–30 wt% NaCl eq.) and homogenization temperatures (63–182°C) measured in fluid inclusions in carbonate, quartz, and sphalerite lie within the typical range of MVT fluid conditions. The good stoichiometry (50–53 mol% CaCO3), low δ18O values (−21 to −14‰ Vienna Peedee belemnite) and relatively high homogenization temperatures (>95°C) of the dolomite suggest the dolomites were formed under burial diagenesis. The ore-forming fluids probably interacted with siliciclastic units, based on elevated Li contents and 87Sr/86Sr ratios, which are highest in the dolomite type after the main ore stage. We propose that the ores formed from the mixing of a downward-infiltrating, sulfur-bearing halite-dissolution fluid with an upward-migrating, metal-rich evaporated seawater fluid, which had already undergone minor mixing with a dilute fluid.  相似文献   

14.
We present Cu isotope data of hypogene and supergene minerals from the Late Paleocene Spence Cu-Mo porphyry in the Atacama Desert of northern Chile. Chalcopyrite displays a restricted range of δ65Cu values within the values reported for primary porphyry Cu sulfides (+ 0.28‰ to + 0.34‰, n = 6). Supergene chalcocite samples show heavier and remarkably homogeneous δ65Cu values, between + 3.91‰ and + 3.95‰ (n = 6), consistent with previous models of Cu leaching and enrichment in porphyry systems. Secondary Cu minerals from the oxide zone show a wider range of composition, varying from + 1.28‰ and + 1.37‰ for chrysocolla (n = 6) to very light Cu isotope signatures reported for atacamite between -5.72‰ to -6.77‰ (n = 17). These data suggest redox cycling of Cu during supergene enrichment of the Spence Cu deposit, characterized by a first stage of supergene chalcocite formation from acidic, isotopically-heavy leach fluids of meteoric origin down-flowing in a semi-arid climate (44 to ~ 15-9 Ma). Reworking of the initial supergene copper assemblage, during the Pleistocene, by rising neutral and chlorine-rich deep formation waters under well-established hyper-arid climate conditions lead to the formation of atacamite with extremely fractionated Cu compositions. Essentially coeval chrysocolla formed by dissolution of atacamite during short episodes of wetter climatic conditions occurring in the latest Pleistocene.  相似文献   

15.
Gossan Hill is an Archean (∼3.0 Ga) Cu–Zn–magnetite-rich volcanic-hosted massive sulfide (VHMS) deposit in the Yilgarn Craton of Western Australia. Massive sulfide and magnetite occur within a layered succession of tuffaceous, felsic volcaniclastic rocks of the Golden Grove Formation. The Gossan Hill deposit consists of two stratigraphically separate ore zones that are stratabound and interconnected by sulfide veins. Thickly developed massive sulfide and stockwork zones in the north of the deposit are interpreted to represent a feeder zone. The deposit is broadly zoned from a Cu–Fe-rich lower ore zone, upwards through Cu–Zn to Zn–Ag–Au–Pb enrichment in the upper ore zone. New sulfur isotope studies at the Gossan Hill deposit indicate that the variation is wider than previously reported, with sulfide δ34S values varying between −1.6 and 7.8‰ with an average of 2.1 ± 1.4‰ (1σ error). Sulfur isotope values have a broad systematic stratigraphic increase of approximately 1.2‰ from the base to the top of the deposit. This variation in sulfur isotope values is significant in view of typical narrow ranges for Archean VHMS deposits. Copper-rich sulfides in the lower ore zone have a narrower range (δ34S values of −1.6 to 3.4‰, average ∼1.6 ± 0.9‰) than sulfides in the upper ore zone. The lower ore zone is interpreted to have formed from a relatively uniform reduced sulfur source dominated by leached igneous rock sulfur and minor magmatic sulfur. Towards the upper Zn-rich ore zone, an overall increase in δ34S values is accompanied by a wider range of δ34S values, with the greatest variation occurring in massive pyrite at the southern margin of the upper ore zone (−1.0 to 7.8‰). The higher average δ34S values (2.8 ± 2.1‰) and their wider range are explained by mixing of hydrothermal fluids containing leached igneous rock sulfur with Archean seawater (δ34S values of 2 to 3‰) near the paleoseafloor. The widest range of δ34S values at the southern margin of the deposit occurs away from the feeder zone and is attributed to greater seawater mixing away from the central upflow zone. Received: 10 June 1999 / Accepted: 28 December 1999  相似文献   

16.
More than 140 middle-small sized deposits or minerals are present in the Weishan-Yongping ore concentration area which is located in the southern part of a typical Lanping strike-slip and pull-apart basin. It has plenty of mineral resources derived from the collision between the Indian and Asian plates. The ore-forming fluid system in the Weishan-Yongping ore concentration area can be divided into two subsystems, namely, the Zijinshan subsystem and Gonglang arc subsystem. The ore-forming fluids of Cu, Co deposits in the Gonglang arc fluid subsystem have δD values between −83.8‰ and −69‰, δ18O values between 4.17‰ and 10.45‰, and δ13C values between −13.6‰ and 3.7‰, suggesting that the ore-forming fluids of Cu, Co deposits were derived mainly from magmatic water and partly from formation water. The ore-forming fluids of Au, Pb, Zn, Fe deposits in the Zijinshan subsystem have δD values between −117.4‰ and −76‰, δ18O values between 5.32‰ and 9.56‰, and Δ13C values between −10.07‰ and −1.5‰. The ore-forming fluids of Sb deposits have δD values between −95‰ and −78‰, δ18O values between 4.5‰ and 32.3‰, and Δ13C values between −26.4‰ and −1.9‰. Hence, the ore-forming fluids of the Zijinshan subsystem must have been derived mainly from formation water and partly from magmatic water. Affected by the collision between the Indian and Asian plates, ore-forming fluids in Weishan-Yongping basin migrated considerably from southwest to northeast. At first, the Gonglang arc subsystem with high temperature and high salinity was formed. With the development of the ore-forming fluids, the Zijinshan subsystem with lower temperature and lower salinity was subsequently formed. Translated from Mineral Deposits, 2006, 25(1): 60–70 [译自: 矿床地质]  相似文献   

17.
Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope （their δ^18O values range from -0.3‰- -0.1‰） and lighter oxygen isotope （their δ^18O values range from -22.1‰- -19.5‰）. Generally, they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water. This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones, preserving intragranular volume and providing the mass basis for later disso- lution caused by acidic fluid flow to produce secondary porosity. Ferriferous calcites are characterized by relatively light carbon isotope with δ^13C values ranging from -8.02‰ to -3.23‰, and lighter oxygen isotope with δ^18O values ranging from -22.9‰ to -19.7‰, which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis. As the mid-late diagenetic products, ferriferous cal- cites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir. The late ankerite is relatively heavy in carbon isotope with δ^13C values ranging from -1.92‰ to -0.84‰, and shows a wide range of variations in oxygen isotopic composition, with δ^18O values ranging from -20.5‰ to -12.6‰. They are believed to have nothing to do with decarboxylation, but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation, and the alkaline diagenetic environment at the mid-late stage would promote this process.  相似文献   

18.
There were strong volcanic and hot spring activities in Late proterozic in the Xiqiu mining district,Zhejiang province,The volcanic rocks and hydrothermal sedimentary cherts have high contents of the major metallogenic elements,Their atomic percentage of Cu:Zn:Pb is similar very much between volcanic rock,hydrothermal sedimentary chert and ore.Therefore,the metallization has a direct bearing on the volcanic and hot spring activities in the Xiqiu area.The δ34S values vary from -6.5‰to 2.8‰,the δ30Si Values from-0.2‰ to 0.6‰,and the δ18O Values from 8.14‰ to 22.32‰,Lead isotopes were derived mainly from the lower crust.The ores have high contents of As,Sb,Bi,Ga,Zn,and Ba,and low Al/(Al Fe Mn)ratios,with Zn/(Zn Pb)ratios approximate to unity,Therefore,the Xiqiu massive copper sulfide deposit can be ascribed to volcano-hot spring deposition.  相似文献   

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

20.
火烧云矿床是我国新发现具有超大型规模的非硫化物铅锌矿床,成因倍受关注.矿床主要由菱锌矿和白铅矿组成,形成块状及少量纹层状和角砾状矿石,构成了层状矿体.赋矿围岩为中侏罗统含沉积石膏的台地相碳酸盐岩,为密西西比河谷型矿床的典型赋矿围岩,而非喷流沉积型矿床的赋矿围岩.矿石中普遍出现被白铅矿交代的方铅矿残留,表明原生矿化为硫化物.方铅矿δ34SV-CDT值为-34‰^-18‰,显示还原硫的来源与细菌还原作用作用有关,这在MVT矿床中较为常见,而在与岩浆作用有关的铅锌矿床中少见.同时,矿床也不具有与岩浆有关的热液矿化和蚀变特征,故矿床的原生硫化物矿化应为MVT型.通过菱锌矿和白铅矿的O同位素组成,计算出形成这两种矿物的流体具有低温、低δ18O值的大气降水的特征,结合白铅矿交代方铅矿的这一现象,表明目前观察到的由菱锌矿和白铅矿构成铅锌矿体系是在表生作用下直接交代原生硫化物矿体形成.  相似文献   

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