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1.
A large number of Paleoproterozoic borate deposits are hosted by the lower units of a volcanic-sedimentary sequence in Liaoning Province, northeastern China, and are a major source of boron in China. The ore-bearing wall rocks in the deposits are serpentinized ultrabasic rocks and carbonates, with layered leptynites, leptites, amphibolites, and migmatites adjacent to the ore. Both the borate ores and country rocks contain tourmaline, although the country rocks have much lower abundances of the mineral. Based on in situ boron isotope measurements using laser ablation–multi-collector–inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS), boron isotope data show that: (1) δ11B values of borate ores range from + 6.8‰ to + 13.9‰ (mean + 10.8‰); (2) tourmalines from the borate ores have δ11B values from + 9.5‰ to + 12.7‰; and (3) the wall rocks within the borate ores yield slightly lower δ11B values ranging from + 5.7‰ to + 7.6‰, and those outside the deposits from − 9.9‰ to − 5.9‰. Positive δ11B values in borates as well as in tourmalines inside the mining area indicate that boron in these Paleoproterozoic borate deposits was derived from marine evaporites. δ34SV-CDT (where V-CDT is Vienna Canyon Diablo Troilite) values of borate ores, serpentinized marbles, and anhydrites range from + 16.1‰ to + 24.7‰, whereas δ13CV-PDB (where V-PDB is Vienna Pee Dee Belemnite) values of marbles range from + 3.2‰ to + 5.9‰. These isotopic characteristics are interpreted to reflect formation in a marine evaporative environment. LA–MC–ICP–MS zircon weighted207Pb/206Pb ages of leptite and serpentinized olivine basalt from the hanging wall of the borate deposits are 2139 ± 13 Ma and 2130 ± 19 Ma, respectively. Therefore, the (~ 2.2 Ga) borate deposits may have originated from marine evaporative boron-bearing sediments, which were interbedded within bimodal volcanic rocks during the early stages of development of the Liaoji rift.  相似文献   

2.
Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε18OSO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent εSO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. δ34SSO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ34SSO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.  相似文献   

3.
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   

4.
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   

5.
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   

6.
This study demonstrates the value of targeted pump and treatment (PAT) to enhance the in situ biodegradation of organic contaminants in groundwater for improved restoration. The approach is illustrated for a plume of phenolic compounds in a sandstone aquifer, where PAT is used for hydraulic containment and removal of dissolved phase contaminants from specific depth intervals. Time-series analysis of the plume hydrochemistry and stable isotope composition of dissolved species (δ34S-SO4, δ13C-CH4, δ13C-TDIC (TDIC = Total Dissolved Inorganic Carbon)) in groundwater samples from high-resolution multilevel samplers were used to deduce changes in the relative significance of biodegradation processes and microbial activity in the plume, induced by the PAT system over 3 years. The PAT system has reduced the maximum contaminant concentrations (up to 6800 mg L−1 total phenols) in the plume by 50% to ∼70% at different locations. This intervention has (i) stimulated in situ biodegradation in general, with an approximate doubling of contaminant turnover based on TDIC concentration, which has increased from <200 mg L−1 to >350 mg L−1, (ii) enhanced the activity of SO4-reducing microorganisms (marked by a declining SO4 concentration with corresponding increase in SO4-δ34S to values >7–14‰V-CDT relative to background values of 1.9–6.5‰V-CDT), and (iii) where the TDIC increase is greatest, has changed TDIC-δ13C from values of −10 to −15‰V-PDB to ∼−20‰V-PDB. This indicates an increase in the relative importance of respiration processes (including denitrification and anaerobic methane oxidation, AMO) that yield 13C-depleted TDIC over fermentation and acetoclastic methanogenesis that yield 13C-enriched TDIC in the plume, leading to higher contaminant turnover. The plume fringe was found to be a zone of enhanced biodegradation by SO4-reduction and methanogenesis. Isotopically heavy methane compositions (up to −47.8‰V-PDB) and trends between δ13C-TDIC and δ13C-CH4 suggest that AMO occurs at the plume fringe where the contaminant concentrations have been reduced by the PAT system. Mass and isotope balances for inorganic carbon in the plume confirm the shift in spatial dominance of different biodegradation processes and significant increase in contribution of anaerobic respiration for contaminant biodegradation in zones targeted by the PAT system. The enhanced in situ biodegradation results from a reduction in organic contaminant concentrations in the plume to levels below those that formerly suppressed microbial activity, combined with increased supply of soluble electron acceptors (e.g. nitrate) into the plume by dispersion. An interruption of the PAT system and recovery of the dissolved organic contaminant concentrations towards former values highlights the dynamic nature of this enhancement on restoration and relatively rapid response of the aquifer microorganisms to changing conditions induced by the PAT system. In situ restoration using this combined engineered and passive approach has the potential to manage plumes of biodegradable contaminants over shorter timescales than would be possible using these methods independently. The application of PAT in this way strongly depends on the ability to ensure an adequate flux of dissolved electron acceptors into the plume by advection and dispersion, particularly in heterogeneous aquifers.  相似文献   

7.
《Applied Geochemistry》2005,20(1):23-39
Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (Tmi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (Th)  = 325 ± 5 °C. The boiling zone shows Th = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO2. Positive clathrate melting temperatures (fusion) with Th = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO2 (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ18O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ18O is due to the rock–water interaction at relatively high temperatures. δ13C stable isotope data show a magmatic source with a minor meteoric contribution for CO2. The initial isotopic value δ34SRES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ34S (FeS2) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ18O.  相似文献   

8.
《Applied Geochemistry》2005,20(11):2017-2037
The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH4, thermogenic C2+ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH4 is bacteriogenic (Calculated δ13CC1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH4. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ13CC1–C = −35.80‰; Hamitabat Field) and Group-3 (δ13C1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C2+ gases. The Group-2 C2+ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ13C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C2+ gases, produced from one field, were generated from isotopically light marine kerogen (δ13C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C2+ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ13C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (Req = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.  相似文献   

9.
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   

10.
The Yukeng–Banling deposit is a typical fault-controlled hydrothermal Cu–Au deposit in the Shanmen Volcanic Basin (SVB), SE China. Ore bodies commonly occur as lodes, lenses and disconnected pods dipping SW with vertical zonation of ore minerals. Ore-related hydrothermal alteration is well developed on both sides of the veins, dominated by silicification, sericitization, chloritization and argillation with a banded alteration zonation. The mineralization can be divided into three stages (stages I, II and III). Native gold is present as veinlets in fractures of fine-grained pyrite from stage II.Zircon U–Pb and Rb–Sr isochron ages indicate that the Cu–Au mineralization is coeval with the Caomen alkaline granite and Xiaokeng quartz-diorite, both emplaced at ca. 102 Ma. Microthermometric measurements of fluid inclusions in quartz and sphalerite from stage II veins indicate that the Yukeng–Banling deposit is an epithermal deposit. Six ore-related quartz grains have δDH2O values of − 69 to − 43‰, and δ18OH2O values calculated using total homogenization temperatures that range from − 2.0 to 0.7‰. All samples plot in an area between the magmatic field and the meteoric line, suggesting that the ore-forming fluids are derived from a mixed source of magmatic and meteoric waters. δ34S values for eight pyrite separates range from − 2.1 to + 4.1‰ with an average of + 1.7‰, and δ34S values for galena and sphalerite are 2.3‰ and 2.2‰, similar to magmatic sulfur. Four alkaline granite samples have Pb isotopic ratios (206Pb/204Pb)t = 18.175–18.411, (207Pb/204Pb)t = 15.652–15.672 and (208Pb/204Pb)t = 38.343–38.800. Three quartz-diorite samples have ratios (206Pb/204Pb)t, (207Pb/204Pb)t and (208Pb/204Pb)t of 18.277–18.451, 15.654–15.693 and 38.673–38.846, respectively. These age-calculated lead isotopic data for alkaline granite are similar to those for the analyzed sulfides. Co/Ni ratios for stage II pyrites range from 1.42 to 5.10, indicating that the Yukeng–Banling deposit records the past involvement of magmatic hydrothermal fluids. The isotope data, together with geological, mineralogical and geochronological evidence, favor a primary magmatic source for sulfur and metals in the ore fluids. Mixing of the Cu- and Au-rich fluids with meteoric water led to precipitation of the Cu–Au veins along NW-trending faults.The Yukeng–Banling deposit, the contemporaneous Caomen alkaline granite and Xiaokeng quartz-diorite in the SVB formed under an extensional setting, due to high-angle subduction of the paleo-Pacific plate. The extensional setting facilitated the formation of Cu- and Au-rich magmas which was derived from enriched mantle and lower crust.  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 Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe3 +–Al3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ11B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe3 +–Al3 + substitution) and δ11B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ11B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ11B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ34SVCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ34SVCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ34SVCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ34SVCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ65CuNBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ65CuNBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ34SVCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.  相似文献   

13.
The İnkaya Cu–Pb–Zn–(Ag) prospect is a typical example of the hydrothermal mineralization occurring in the Menderes Massif, which crop out in Western Anatolia. The prospect located approximately 20 km west of Simav (Kütahya-Turkey) in northern part of the Menderes Massif have been characterized through the detailed examinations involving geological, mineralogical, whole-rock geochemistry, fluid inclusion, stable isotope and lead isotope.The İnkaya Cu–Pb–Zn–(Ag) prospect is located along an E–W-trending fault in the Cambrian Simav Metamorphics, which consist of quartz–muscovite schist, quartz–biotite schist, muscovite schist, biotite schist and the Arıkayası Formation, which is composed of marbles. Galena, sphalerite, chalcopyrite, pyrite and fahlore are the main minerals, and they are accompanied by small amounts of cerussite, anglesite, digenite, enargite, chalcocite, covellite, bornite, and Fe-oxides with gangue quartz. In addition to Pb, Zn, Cu, Ag, the ore samples contain substantial quantities of As, Cd and Bi and small amount of Au. Average contents of Cu, Pb, Zn and Ag are 77,400 ppm, 102,600 ppm, 6843 ppm and 203 ppm, respectively.The δ34S values for galena, chalcopyrite and pyrite formed in the same stage vary in the range from − 1.7 to − 2.1‰ (average − 2.0), 0.1 to 0.3‰ (average 0.2) and − 1.5 to 2.6‰ (average + 1.5), respectively.δ34S values for H2S, representing the composition of the fluids responsible for the sulfide mineral formations and calculated from the δ34S value are between − 2.77 and 1.33‰; it is consistent with the sulfur in sulfide minerals. δ18Oquartz values range from 11.3 to 16.4‰ and estimated δ18Ofluid values range from 5.4 to 10.6‰.Pyrite–galena and pyrite–chalcopyrite pairs calculated to determine equilibrium isotope temperatures based on δ34S values are between 254.6 and 277.4 °C for pyrite–galena and 274.7 °C for pyrite–chalcopyrite. Sulfur and oxygen isotope values similar to the values for fluid equilibrated with an felsic magmatic source.Fluid inclusion studies on quartz of the same silicification stage coexisting with galena, sphalerite and chalcopyrite collected from the mineralized vein indicate that the temperature range of the fluids is 235 °C to 340 °C and that the salinities are 0.7 to 4.49 wt.% NaCl equivalent. The wide range of homogenization temperatures and relatively lower salinities of the fluid inclusions indicate that at least two different fluid generations were trapped in the quartz from only one fluid type. Also, lower salinities of fluid inclusion probably indicate mixing of meteoric water and magmatic fluid.The galena has 206Pb/204Pb values of 18.862–18.865, 207Pb/204Pb values of 15.707–15.711, and 208Pb/204Pb values of 39.033–39.042. The lead isotope values show a similarity with upper crustal values.  相似文献   

14.
The polymetallic Mykonos vein system in the Cyclades, Greece, consists of 15 tension-gashes filled with barite, quartz, pyrite, sphalerite, chalcopyrite and galena in ca. 13.5 Ma, I-type, Mykonos monzogranite. Zones of silica and chlorite–muscovite alteration are associated with the veins and overprint pervasive silicification, phyllic and argillic alteration that affected large parts of the monzogranite. The mineralization cements breccias and consists of an early barite–silica–pyrite–sphalerite–chalcopyrite assemblage followed by later argentiferous galena. A combination of fluid inclusion and stable isotope data suggests that the barite and associated mineralization were deposited from fluids containing 2 to 17 wt.% NaCl equivalent, at temperatures of ~ 225° to 370 °C, under a hydrostatic pressure of ≤ 100 bars. The mineralizing fluids boiled and were saturated in H2S and SO2.Calculated δ18OH2O and δDH2O, initial 87Sr/86Sr isotope compositions and the trace and REEs elements contents are consistent with a model in which the mineralizing fluids were derived during alteration of the Mykonos intrusion and subsequently mixed with Miocene seawater. Heterogeneities in the calculated δ34SSO4− 2 and δ34SH2S compositions of the ore fluids indicate two distinct sources for sulfur, namely of magmatic and seawater origin, and precipitation due to reduction of the SO4− 2 during fluid mixing. The physicochemical conditions of the fluids were pH = 5.0 to 6.2, logfS2 = − 13.8 to − 12.5, logfO2 = − 31.9 to − 30.9, logfH2S(g) = − 1.9 to − 1.7, logfTe2 = − 7.9 and logα(SO4− 2(aq)/H2S(aq)) = + 2.6 to + 5.5. We propose that retrograde mesothermal hydrothermal alteration of the Mykonos monzogranite released barium and silica from the alkali feldspars. Barite was precipitated due to mixing of SO4− 2-rich Miocene seawater with the ascending Ba-rich magmatic fluid venting upwards in the pluton.  相似文献   

15.
The Maevatanana gold deposit in Madagascar is hosted by Archean metamorphic rocks in quartz–sulfide veins that are structurally controlled by NNW–SSE trending shear zones. Fluid inclusion data show that the trapping conditions in quartz range from 0.87 to 2.58 kbar at temperatures of 269–362 °C. Laser Raman spectroscopy confirms that these inclusions consist of CO2, SO2, and H2O. The δ34S values of the pyrites range from 1.7‰ to 3.6‰, with an average of 2.25‰, supporting a magmatic origin. Noble gases (He, Ne, Ar, Ke, Xe) are chemically inert, thus will not be involved in chemical reactions during geological processes. Also due to the low concentration of He in the atmosphere and the low solubility of He in aqueous fluids, the atmosphere-derived He is unlikely to significantly affect He abundances and isotopic ratios of crustal fluids, ensures that He production should have the typical crust 3He/4He ratios. The 3He/4He ratios of fluid inclusions in pyrite from the deposit range from 0.06 to 0.12 Ra, while the 40Ar/36Ar ratios range from 6631 to 11441. We infer that the ore-forming fluids could have been exsolved from a granitic magma. The oxygen and hydrogen isotope compositions of the ore-forming fluids (1.5‰ ≤ δ18OH2O ≤ 7.8‰; –72‰ ≤ δD ≤ –117‰) indicate they were derived from a granitic magma. Four pyrite samples from the gold deposit yield a precise Re–Os isochron age of 534 ± 13 Ma. Given that the post-collisional granites in northern and central Madagascar were derived by melting of sub-continental lithospheric mantle and formed between 537 and 522 Ma, we can state that the gold metallogenesis was coeval with the crystallization age of these parental magmas. These data could be accounted for the formation of the Maevatanana gold deposit. First, the shear zones hosting the deposit formed around 2.5 Ga, when the Madagascan micro-continental blocks collided with other continental blocks, triggering large-scale tectono-magmatic activity and forming NNW–SSE trending shear zones. The gold mineralization at Maevatanana is coeval with the crystallization age of the Cambrian post-collisional A-type granitoid plutons in northern and central Madagascar, implying that this deposit is associated with extensional collapse of the East African Orogen. This extension in turn induced asthenospheric upwelling, melting of sub-continental lithospheric mantle. These magmas underplated the lower crust, generating voluminous granitic magmas by partial melting of the lower crust. The mixing magma during tectono-thermal reactivation of the East African Orogen produced large volumes of volatiles that extracted gold from the granitic magma and produced Au–S complexes (e.g., Au(HSO3)2−). The shear zones, which were then placed under extensional collapse of the East African Orogen in the Cambrian, formed favorable pathways for the magmatic ore-forming fluids. These fluids then precipitated gold-sulfides that form the Maevatanana gold deposit.  相似文献   

16.
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   

17.
The large (>180 Kt WO3 and at least 10–15 t Au) Vostok-2 deposit is situated in a metallogenic belt of W, Sn-W, Au, and Au-W deposits formed in late to post-collisional tectonic environment after cessation of active subduction. The deposit is related to an ilmenite-series high-K calc-alkaline plutonic suite that, by its petrologic signatures, is transitional between those at W-dominant and Au-dominant reduced intrusion-related deposits. Consistently, besides large W-Cu skarns of the reduced type, the deposit incorporates quartz stockworks with significant Au-W-Bi mineralization also formed in a reduced environment. The hydrothermal stages include prograde and retrograde, essentially pyroxene skarns, hydrosilicate (amphibole, chlorite, quartz) alteration, and phyllic (quartz, sericite, albite, apatite, and carbonate) alteration assemblages. These assemblages contain abundant scheelite associated with pyrrhotite, chalcopyrite and, at the phyllic stage, also with Bi minerals, As-Bi-Sb-Te-Pb-Zn sulfides and sulfosalts, as well as Au mineralization. The fluid evolution included hot, high-pressure (420–460 °C, 1.1–1.2 kbar), low-salinity (5.4–6.0 wt% NaCl-equiv.) aqueous fluids at the retrograde skarn stage, followed by lower temperature cyclic releases of high-carbonic, low salinity to non-carbonic moderate-salinity aqueous fluids. At the hydrosilicate stage, a high-carbonic, CH4-dominated, hot (350–380 °C) low salinity fluid was followed by cooler (300–350 °C) non-carbonic moderate-salinity (5.7–14.9 wt% NaCl-equiv.) fluid. At the phyllic stage, a high-carbonic, CO2-dominated, moderately-hot (330–355 °C, 0.9 kbar) low salinity fluid was followed by cooler (230–265 °C) non-carbonic moderate-salinity (6.6–12.0 wt% NaCl-equiv.) fluid. A homogenized magmatic source of water (δ18OH2O = +8.3 to +8.7‰), and a sedimentary source of sulfur (δ34S = −6.9 to −6.2‰) and carbon (δ13Cfluid = −20.1 to −14.9‰) at the hydrosilicate stage are suggested. A magmatic source of water (δ18O = +8.6 to +9.2‰) and a sedimentary source of sulfur (δ34S = −9.3 to −4.1‰) but a magmatic (mantle- to crustal-derived) source of carbon (δ13Cfluid = −6.9 to −5.2‰) are envisaged for fluids that formed the early mineral assemblage of the phyllic stage. Then, the role of sedimentary carbon again increased toward the intermediate (δ13Cfluid = −16.4 to −14.5‰) and late (δ13Cfluid = −16.3 to −14.7‰) phyllic mineral assemblages. The magmatic differentiation was responsible for the fluid enrichment in W, whereas Au and Bi could also have been sourced from mafic magma. The decreasing temperatures, together with elevated Ca content in non-boiling fluids, promoted scheelite deposition at the early hydrothermal stages. The most intense scheelite deposition at the phyllic stage was caused by CO2 removal due to boiling of CO2-rich fluids; further cooling of non-boiling fluids favoured joint deposition of scheelite, Bi and Au.  相似文献   

18.
Copper and iron skarn deposits are economically important types of skarn deposits throughout the world, especially in China, but the differences between Cu and Fe skarn deposits are poorly constrained. The Edong ore district in southeastern Hubei Province, Middle–Lower Yangtze River metallogenic belt, China, contains numerous Fe and Cu–Fe skarn deposits. In this contribution, variations in skarn mineralogy, mineralization-related intrusions and sulfur isotope values between these Cu–Fe and Fe skarn deposits are discussed.The garnets and pyroxenes of the Cu–Fe and Fe skarn deposits in the Edong ore district share similar compositions, i.e., dominantly andradite (Ad29–100Gr0–68) and diopside (Di54–100Hd0–38), respectively. This feature indicates that the mineral compositions of skarn silicate mineral assemblages were not the critical controlling factors for variations between the Cu–Fe and Fe skarn deposits. Intrusions associated with skarn Fe deposits in the Edong ore district differ from those Cu–Fe skarn deposits in petrology, geochemistry and Sr–Nd isotope. Intrusions associated with Fe deposits have large variations in their (La/Yb)N ratios (3.84–24.6) and Eu anomalies (δEu = 0.32–1.65), and have relatively low Sr/Y ratios (4.2–44.0) and high Yb contents (1.20–11.8 ppm), as well as radiogenic Sr–Nd isotopes (εNd(t) = − 12.5 to − 9.2) and (87Sr/86Sr)i = 0.7067 to 0.7086. In contrast, intrusions associated with Cu–Fe deposits are characterized by relatively high Sr/Y (35.0–81.3) and (La/Yb)N (15.0–31.6) ratios, low Yb contents (1.00–1.62 ppm) without obvious Eu anomalies (δEu = 0.67–0.97), as well as (87Sr/86Sr)i = 0.7055 to 0.7068 and εNd(t) = − 7.9 to − 3.4. Geochemical evidence indicates a greater contribution from the crust in intrusions associated with Fe skarn deposits than in intrusions associated with Cu–Fe skarn deposits. In the Edong ore district, the sulfides and sulfates in the Cu–Fe skarn deposits have sulfur isotope signatures that differ from those of Fe skarn deposits. The Cu–Fe skarn deposits have a narrow range of δ34S values from − 6.2‰ to + 8.7‰ in sulfides, and + 13.2‰ to + 15.2‰ in anhydrite, while the Fe skarn deposits have a wide range of δ34S values from + 10.3‰ to + 20.0‰ in pyrite and + 18.9‰ to + 30.8‰ in anhydrite. Sulfur isotope data for anhydrite and sedimentary country rocks suggest that the formation of skarns in the Edong district involved the interaction between magmatic fluids and variable amounts of evaporites in host rocks.  相似文献   

19.
The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ34S range between ?29.8 and + 10.2‰ and Δ33S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ34SCRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ34S and Δ33S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ34S and Δ33S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ34S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO2 contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.  相似文献   

20.
Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (65Cu/63Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (56Fe/54Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ65Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ56Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ56Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.  相似文献   

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