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1.
Hg in hydrothermal systems is generally thought to be transported as Hg-S complexes. However, the abundance of Hg0vap, in geothermal emissions suggests that Hg0eq, is present in the liquid phase of geothermal systems. Calculations for reducing fluids (HS? dominant over SO=4) in equilibrium with cinnabar indicate that Hg0eq, can be quite abundant relative to other species at temperatures above 200°C. Increasing pH and temperature, and decreasing total S, ionic strength, and pO2 all promote the abundance of Hg0eq. When a vapor phase develops from a geothermal liquid, Hg partitions strongly into the vapor as Hg0vap. Vapor transport at shallow level then results in the formation of Hg halos around shallow aquifers as well as in a flux of Hg to the atmosphere. Hg deposition may occur in response to mixing with oxidizing or acidic water, turning Hg0eq, into Hg++, with subsequent cinnabar precipitation. When pyrite is the stable Fe-sulfide, cinnabar solubility is at its lowest, so cinnabar + pyrite assemblages are common. Cinnabar + hematite ± pyrite can precipitate from more oxidized or S-poor water. Hg0liq, can occur as a primary mineral, in coexistence with all common Fe-sulfides and oxides. Cinnabar ± Hg0liq cannot coexist with pyrrhotite or magnetite at temperatures between 100° and 250°C. Evidence from Hg deposits indicates that many formed from dilute hydrothermal fluids in which Hg probably occurred as Hg0eq. In S-rich systems, Hg may occur as Hg-S complexes, and in saline waters it can occur as Hg-Cl complexes.  相似文献   

2.
Mining wastes and calcines from two abandoned mining areas (Valle del Azogue and Bayarque in Almería) have been characterized. In the mining wastes, the dominant mercury phases are cinnabar and elemental mercury in the matrix. In the calcines, however, the dominant mercury phase is elemental mercury bounded to the matrix. Water-leaching experiments were conducted on low-grade stockpiles and calcines in order to simulate the mobilization of mercury by runoff under environmental conditions. The laboratory column-leaching experiments show a possible mobilization of mercury from Hg0 dissolution, colloid transport and a possible dissolution of calomel and other soluble phases in the mine wastes from the Valle del Azogue and Bayarque mines. Equilibrium speciation modeling of Hg, conducted using the numerical code MINTEQ, showed that the theoretical dominant mercury species in the calcine and mining wastes samples are Hg(OH)2, HgCl2, HgClOH and Hg0. In some leachates obtained from the Valle del Azogue mining wastes (sample A06), the high Hg concentrations may indicate the possible dissolution of mineral phases such as calomel and other soluble phases, which are subsaturated. The environmental results indicate a great environmental mobility of mercury, especially during wet episodes associated with intense precipitation events, when there are significative amounts of secondary soluble minerals.  相似文献   

3.
Five hundred years of mercury (Hg) mining activity in Idrija, Slovenia caused widespread Hg contamination. Besides Hg emissions from the ore smelter, tailings have been found to be the major source of river sediment contamination. In the present study, solid phase binding forms and the aqueous mobility of Hg have been investigated in tailings of the Idrija Hg mine by means of a pyrolysis technique and aqueous Hg speciation. Results show that Hg binding forms differ with the age of the tailings due to the processing of different ores with different roasting techniques. In older tailings, the predominant Hg species is cinnabar (HgS), due to incomplete roasting, whereas in tailings of the 20th century the amount of cinnabar in the material decreased due to a higher efficiency of the roasting process and the increasing use of ores bearing native Hg. In younger tailings, metallic Hg (Hg0) sorbed to mineral matrix components such as dolomite and Fe-oxyhydroxides became the predominant Hg binding form in addition to unbound Hg0 and traces of HgO. Leaching tests show that in younger tailings high amounts of soluble Hg exist in reactive form. In older tailings most of the soluble Hg occurs bound to soluble complexes. It might be assumed that in the long term, matrix-bound Hg0 could be bound to humic acids derived from soils covering the tailings. This means that, despite the lower total Hg concentrations found in the younger tailings, the long-term risk potential of its mobile matrix-bound Hg0 is higher than that of older tailings bearing mostly immobile cinnabar.  相似文献   

4.
Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg2+ and CH3Hg+ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg2+ is strongly dependent on complexation to dissolved organic matter, the solubility of CH3Hg+ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH3Hg+. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.  相似文献   

5.
The giant Almadén mercury deposit (Spain) is hosted by the Lower Silurian Criadero Quartzite; in turn this ore-bearing rock unit is cross-cut by the so-called Frailesca unit, a diatreme body of basaltic composition. The geochemical characteristics of the Silurian to Devonian Almadén District volcanic units indicate that these rocks originated from an enriched, evolving mantle source that ultimately yielded basanites–nephelinites to rhyolites, through olivine-basalts, pyroxene-basalts, trachybasalts, trachytes, very scarce rhyolites, and quartz-diabases. The Silurian intraplate alkaline volcanism developed in submarine conditions which triggered widespread hydrothermal activity resulting in Hg ore formation and pervasive alteration to carbonates. The δ18O, δ13C, and δ34S isotopic signatures for carbonates and pyrite suggest different sources for carbon and sulfur, including magmatic and organic for the former and magmatic and sea water for the latter. The most important and efficient natural source of mercury on Earth is by far the volcanic activity, which liberates mercury via quiescent degassing and catastrophic (Plinian) events when eruptions can overwhelm the atmospheric budget of Hg. Thus, we suggest that CO2 degasification and coeval distillation of mercury from the volcanic rocks fed the huge hydrothermal system that led to massive deposition of mercury at Almadén. Build up of Hg0gas in magmatic chambers during waning rifting in the Late Ordovician, followed by renewed volcanism in the Early Silurian, would have resulted in massive degasification of the accumulated mercury. Part of this mercury went into the Criadero Quartzite leading to formation of the huge Almadén deposit and others (e.g., El Entredicho) along the same stratigraphic level. Progressive depletion of the deep seated magmatic Hg stock would have resulted in a drastic reduction in ore deposit size after the Lower Silurian when smaller deposits formed (e.g., Las Cuevas).  相似文献   

6.
The Xuebaoding crystal deposit, located in northern Longmenshan, Sichuan Province, China, is well known for producing coarse‐grained crystals of scheelite, beryl, cassiterite, fluorite and other minerals. The orebody occurs between the Pankou and Pukouling granites, and a typical ore vein is divided into three parts: muscovite and beryl within granite (Part I); beryl, cassiterite and muscovite in the host transition from granite to marble (Part II); and the main mineralization part, an assemblage of beryl, cassiterite, scheelite, fluorite, apatite and needle‐like tourmaline within marble (Part III). No evidence of crosscutting or overlapping of these ore veins by others suggests that the orebody was formed by single fluid activity. The contents of Be, W, Sn, Li, Cs, Rb, B, and F in the Pankou and Pukouling granites are similar to those of the granites that host Nanling W–Sn deposits. The calculated isotopic compositions of beryl, scheelite and cassiterite (δD, ?69.3‰ to ?107.2‰ and δ18OH2O, 8.2‰ to 15.0‰) indicate that the ore‐forming fluids were mainly composed of magmatic water with minor meteoric water and CO2 derived from decarbonation of marble. Primary fluid inclusions are CO2? CH4+ H2O ± CO2 (vapor), with or without clathrates and halites. We estimate the fluid trapping condition at T = 220 to 360°C and P > 0.9 kbar. Fluid inclusions are rich in H2O, F and Cl. Evidence for fluid‐phase immiscibility during mineralization includes variable L/V ratios in the inclusions and inclusions containing different phase proportions. Fluid immiscibility may have been induced by the pressure released by extension joints, thereby facilitating the mineralization found in Part III. Based on the geochemical data, geological occurrence, and fluid inclusion studies, we hypothesize that the coarse‐grained crystals were formed by: (i) the high content of ore elements and volatile elements such as F in ore‐forming fluids; (ii) occurrence of fluid immiscibility and Ca‐bearing minerals after wall rock transition from granite to marble making the ore elements deposit completely; (iii) pure host marble as host rock without impure elements such as Fe; and (iv) sufficient space in ore veins to allow growth.  相似文献   

7.
The Mayuan stratabound Pb-Zn deposit in Nanzheng,Shaanxi Province,is located in the northern margin of the Yangtze Plate,in the southern margin of the Beiba Arch.The orebodies are stratiform and hosted in breciated dolostone of the Sinian Dengying Formation.The ore minerals are primarily sphalerite and galena,and the gangue minerals comprise of dolomite,quartz,barite,calcite and solid bitumen.Fluid inclusions from ore-stage quartz and calcite have homogenization tempreatures from 98 to 337℃ and salinities from 7.7 wt%to 22.2 wt%(NaCl equiv.).The vapor phase of the inclusions is mainly composed of CH_4 with minor CO_2 and H_2S.The δD_(fluid) values of fluid inclusions in quartz and calcite display a range from-68‰ to-113‰(SMOW),and the δ~(18)O_(fluid)values calculated from δ~(18)O_(quartz) and δ~(18)O_(calcite) values range from 4.5‰ to 16.7‰(SMOW).These data suggest that the ore-forming fluids may have been derived from evaporitic sea water that had reacted with organic matter.The δ~(13)C_(CH4) values of CH_4 in fluid inclusions range from-37.2‰ to-21.0‰(PDB),suggesting that the CH_4 in the ore-forming fluids was mainly derived from organic matter.This,together with the abundance of solid bitumen in the ores,suggest that organic matter played an important role in mineralization,and that the thermochemical sulfate reduction(TSR) was the main mechanism of sulfide precipitation.The Mayuan Pb-Zn deposit is a carbonate-hosted epigenetic deposit that may be classified as a Mississippi Valley type(MVT) deposit.  相似文献   

8.
Classic porphyry Cu–Mo deposits are mostly characterized by close temporal and spatial relationships between Cu and Mo mineralization. The northern Dabate Cu–Mo deposit is a newly discovered porphyry Cu–Mo polymetallic deposit in western Tianshan, northwest China. The Cu mineralization postdates the Mo mineralization and is located in shallower levels in the deposit, which is different from most classic porphyry Cu–Mo deposits. Detailed field investigations, together with microthermometry, laser Raman spectroscopy, and O‐isotope studies of fluid inclusions, were conducted to investigate the origin and evolution of ore‐forming fluids from the main Mo to main Cu stage of mineralization in the deposit. The results show that the ore‐forming fluids of the main Mo stage belonged to an NaCl + H2O system of medium to high temperatures (280–310°C) and low salinities (2–4 wt% NaCl equivalent (eq.)), whereas that of the main Cu stage belonged to an F‐rich NaCl + CO2 + H2O system of medium to high temperatures (230–260°C) and medium to low salinities (4–10 wt% NaCl eq.). The δ18O values of the ore‐forming fluids decrease from 3.7–7.8‰ in the main Mo stage to ?7.5 to ?2.9‰ in the main Cu stage. These data indicate that the separation of Cu and Mo was closely related to a large‐scale vapor–brine separation of the early ore‐forming fluids, which produced the Mo‐bearing and Cu‐bearing fluids. Subsequently, the relatively reducing (CH4‐rich) Mo‐bearing, ore‐forming fluids, dominantly of magmatic origin, caused mineralization in the rhyolite porphyry due to fluid boiling, whereas the relatively oxidizing (CO2‐rich) Cu‐bearing, ore‐forming fluids mixed with meteoric water and precipitated chalcopyrite within the crushed zone at the contact between rhyolite porphyry and wall rock. We suggest that the separation of Cu and Mo in the deposit may be attributed to differences in the chemical properties of Cu and Mo, large‐scale vapor–brine separation of early ore‐forming fluids, and changes in oxygen fugacity.  相似文献   

9.
The Chitudian Zn‐Pb ore deposit, Luanchuan, Henan province, was recently discovered in the southern margin of the North China Craton. The Zn‐Pb orebodies are hosted in the Proterozoic Guandaokou and Luanchuan Groups, occurring as veins in interbedding fracture zones mainly in a WNW‐ and partially in a NS‐direction. The Zn‐Pb ores are characterized by banded, massive, and breccia structures, coarse crystal grains, and a simple mineral composition mainly of galena, sphalerite, pyrite, quartz, dolomite, and calcite. In addition to the vein type orebodies, there are Mo‐ and Zn‐bearing skarn orebodies in the northwest of the Chitudian ore field. Four types of primary fluid inclusions in quartz and calcite were recognized in the Chitudian Zn‐Pb ores, including aqueous, aqueous‐CO2, daughter‐mineral‐bearing aqueous, and daughter‐mineral‐bearing aqueous‐CO2 inclusions, with aqueous inclusion being most common. The homogenization temperatures of the fluid inclusions from the main mineralization stage are from 290°C to 340°C, and the salinities mainly from 3.7 to 14.8 wt% NaCl equivalent. In addition to CO2, CH4 and H2S were detected in the vapor phase and HS in the liquid phase of the fluid inclusions by Laser Raman spectroscopy. The δ34SV‐CDT values of ore sulfides from the Chitudian deposit range from ?0.32‰ to 8.30‰, and show two modal peaks in the histogram, one from 1‰ to 4‰, and the other from 5‰ to 7‰. The former peak is similar to that of porphyry‐type Mo‐W deposits in the area, whereas the latter is relatively close to the sulfur in the strata. The ore sulfur may have been derived from both the magma and the strata. The Pb‐isotopic compositions of the ore minerals from Chitudian, with 206Pb/204Pb from 17.005 to l7.953, 207Pb/204Pb from 15.414 to 15.587, and 208Pb/204Pb from 37.948 to 39.036, are similar to those of Mesozoic porphyries in the Chitudian ore field, suggesting that the ore‐forming metals were mainly derived from the Mesozoic magmatic intrusions. The Chitudian Zn‐Pb deposit is interpreted to be a distal hydrothermal vein‐type deposit, which was genetically related to the proximal, skarn‐type Mo ore deposits in the region.  相似文献   

10.
The Xiaojiashan tungsten deposit is located about 200 km northwest of Hami City, the Eastern Tianshan orogenic belt, Xinjiang, northwestern China, and is a quartz vein‐type tungsten deposit. Combined fluid inclusion microthermometry, host rock geochemistry, and H–O isotopic compositions are used to constrain the ore genesis and tectonic setting of the Xiaojiashan tungsten deposit. The orebodies occur in granite intrusions adjacent to the metamorphic crystal tuff, which consists of the second lithological section of the first Sub‐Formation of the Dananhu Formation (D2d 12). Biotite granite is the most widely distributed intrusive bodies in the Xiaojiashan tungsten deposit. Altered diorite and metamorphic crystal tuff are the main surrounding rocks. The granite belongs to peraluminous A‐type granite with high potassic calc‐alkaline series, and all rocks show light Rare Earth Element (REE)‐enriched patterns. The trace element characters suggest that crystallization differentiation might even occur in the diagenetic process. The granite belongs to postcollisional extension granite, and the rocks formed in an extensional tectonic environment, which might result from magma activity in such an extensional tectonic environment. Tungsten‐bearing quartz veins are divided into gray quartz vein and white quartz veins. Based on petrography observation, fluid inclusions in both kinds of vein quartz are mainly aqueous inclusions. Microthermometry shows that gray quartz veins have 143–354°C of Th, and white quartz veins have 154–312°C of Th. The laser‐Raman test shows that CO2 is found in fluid inclusions of the tungsten‐bearing quartz veins. Quadrupole mass spectrometry reveals that fluid inclusions contain major vapor‐phase contents of CO2, H2O. Meanwhile, fluid inclusions contain major liquid‐phase contents of Cl?, Na+. It can be speculated that the ore‐forming fluid of the Xiaojiashan tungsten deposit is characterized by an H2O–CO2, low salinity, and H2O–CO2–NaCl system. The range of hydrogen and oxygen isotope compositions indicated that the ore‐forming fluids of the tungsten deposit were mainly magmatic water. The ore‐forming age of the Xiaojiashan deposit should to be ~227 Ma. During the ore‐forming process, the magmatic water had separated from magmatic intrusions, and the ore‐bearing complex was taken to a portion where tungsten‐bearing ores could be mineralized. The magmatic fluid was mixed by meteoric water in the late stage.  相似文献   

11.
Pristine water bodies in the Negro River basin, Brazilian Amazon, show relatively high concentrations of mercury. These waters are characterized by acidic pH, low concentrations of suspended solids, and high amounts of dissolved organic matter and are exposed to intense solar radiation throughout the year. This unique environment creates a very dynamic redox chemistry affecting the mobility of mercury due to the formation of the dissolved elemental species (Hg0). It has been shown that in this so-called black water, labile organic matter from flooded forest is the major scavenger of photogenerated H2O2. In the absence of hydrogen peroxide, these black waters lose their ability to oxidize Hg0 to Hg2+, thus increasing Hg0 evasion across the water/atmosphere interface, with average night time values of 3.80 pmol m?2 h?1. When the dry period starts, labile organic matter inputs gradually diminish, allowing the increasing concentration of H2O2 to re-establish oxidative water conditions, inhibiting the metal flux across the water/atmosphere interface and contributing to mercury accumulation in the water column.  相似文献   

12.
The Haobugao deposit, located in the southern segment of the Great Xing'an Range, is a famous skarn‐related Pb‐Zn‐(Cu)‐(Fe) deposit in northern China. The results of our fluid inclusion research indicate that garnets of the early stage (I skarn stage) contain three types of fluid inclusions (consistent with the Mesozoic granites): vapor‐rich inclusions (type LV, with VH2O/(VH2O + LH2O) < 50 vol %, and the majority are 5–25 vol %), liquid‐rich two‐phase aqueous inclusions (type VL, with VH2O/(VH2O + LH2O) > 50 vol %, the majority are 60–80 vol %), and halite‐bearing multiphase inclusions (type SL). These different types of fluid inclusions are totally homogenized at similar temperatures (around 320–420°C), indicating that the ore‐forming fluids of the early mineralization stage may belong to a boiling fluid system. The hydrothermal fluids of the middle mineralization stage (II, magnetite‐quartz) are characterized by liquid‐rich two‐phase aqueous inclusions (type VL, homogenization temperatures of 309–439°C and salinities of 9.5–14.9 wt % NaCl eqv.) that coexist with vapor‐rich inclusions (type LV, homogenization temperatures of 284–365°C and salinities of 5.2–10.4 wt % NaCl eqv.). Minerals of the late mineralization stage (III sulfide‐quartz stage and IV sulfide‐calcite stage) only contain liquid‐rich aqueous inclusions (type VL). These inclusions are totally homogenized at temperatures of 145–240°C, and the calculated salinities range from 2.0 to 12.6 wt % NaCl eqv. Therefore, the ore‐forming fluids of the late stage are NaCl‐H2O‐type hydrothermal solutions of low to medium temperature and low salinity. The δD values and calculated δ18OSMOW values of ore‐forming fluids of the deposit are in the range of ?4.8 to 2.65‰ and ?127.3‰ to ?144.1‰, respectively, indicating that ore‐forming fluids of the Haobugao deposit originated from the mixing of magmatic fluid and meteoric water. The S‐Pb isotopic compositions of sulfides indicate that the ore‐forming materials are mainly derived from underlying magma. Zircon grains from the mineralization‐related granite in the mining area yield a weighted 206Pb/238U mean age of 144.8 ±0.8 Ma, which is consistent with a molybdenite Re‐Os model age (140.3 ±3.4 Ma). Therefore, the Haobugao deposit formed in the Early Cretaceous, and it is the product of a magmatic hydrothermal system.  相似文献   

13.
We combined synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy and binding affinity studies to determine the coordination, geometry, and strength of methyl mercury, CH3Hg (II), bonding in soil and stream organic matter. Samples of organic soil (OS), potentially soluble organic substances (PSOS) from the soil, and organic substances from a stream (SOS) draining the soil were taken along a short “hydrological transect.” We determined the sum of concentrations of highly reduced organic S groups (designated Org-SRED), such as thiol (RSH), disulfane (RSSH), sulfide (RSR), and disulfide (RSSR), using sulfur K-edge XANES. Org-SRED varied between 27% and 64% of total S in our samples. Hg LIII-edge EXAFS analysis were determined on samples added CH3Hg (II) to yield CH3Hg (II)/Org-SRED ratios in the range 0.01-1.62. At low ratios, Hg was associated to one C atom (the methyl group) at an average distance of 2.03 ± 0.02 Å and to one S atom at an average distance of 2.34 ± 0.03 Å, in the first coordination shell. At calculated CH3Hg(II)/Org-SRED ratios above 0.37 in OS, 0.32 in PSOS, and 0.24 in SOS, the organic S sites were saturated by CH3Hg+, and O (and/or N) atoms were found in the first coordination shell of Hg at an average distance of 2.09 ± 0.01 Å. Based on the assumption that RSH (and possibly RSSH) groups take part in the complexation of CH3Hg+, whereas RSSR and RSR groups do not, approximately 17% of total organic S consisted of RSH (+ RSSH) functionalities in the organic soil. Corresponding figures for samples PSOS and SOS were 14% and 9%, respectively. Competitive complexation of CH3Hg+ by halide ions was used to determine the average binding strength of native concentrations of CH3Hg (II) in the OS sample. Using data for Org-SRED, calculated surface complexation constants were in the range from 1016.3 to 1016.7 for a model RSH site having an acidity constant of mercaptoacetic acid. These values compare favorably with identically defined stability constants (log K1) for the binding of methyl mercury to thiol groups in well-defined organic compounds.  相似文献   

14.
The Gaogangshan Mo deposit, located in the northern part of the Lesser Xing'an Range (the eastern part of the Xing'an–Mongolia Orogenic Belt), is one of the newly discovered Mo deposits in northeast China. Ore bodies occur in the granite and are generally in vein and stockwork forms. Major metallic minerals in the ore include pyrite and molybdenite. The styles of mineralization are disseminated, veinlet–disseminated, and veinlet. The major types of wall–rock alteration are silicification–potassic alteration, phyllic alteration and propylitization. Fluid inclusion analyses indicate that the ore‐forming fluid during the major mineralization stage is an H2O–NaCl–CO2 system, with wide homogenization temperature and salinity ranges. The abundant CO2–rich and coexisting halite–bearing fluid inclusion assemblages in the main stage of mineralization highlight the significance of intensive fluid boiling for porphyry Mo mineralization. Comprehensive study of the ore‐forming conditions, geological features of the deposit, micro‐thermometric analysis of fluid inclusions and comparison of the Gaogangshan deposit with other typical porphyry deposits leads to the conclusion that the deposit is a porphyry type. We obtained a weighted mean age of the molybdenite deposit at Gaogangshan of 250.7 ± 1.8 Ma. The isotopic dating results indicate that the Gaogangshan deposit was formed in the Permo–Triassic, which is the earliest Mo–only deposit in northeast China. The formation of the Gaogangshan Mo deposit may be related to the extension and break–up of the Songnen Block and Jiamusi Block in the Permo–Triassic.  相似文献   

15.
This report presents mineralogical, geochemical and isotopic data on samples obtained using the Benthic Multi‐coring System (BMS) to drill a submarine hydrothermal deposit developed in a caldera on the summit of the Suiyo Seamount in the Izu–Bonin Island Arc, south of Japan. This deposit is regarded as the first example of Kuroko‐type sulfide mineralization on a volcano at the volcanic front of an island arc. The mineralization and hydrothermal alteration below the 300 × 150‐m area of active venting was investigated to depths of 2–9 m below the sea floor. Drilling beneath the area of active venting recovered a sequence of altered volcanic rocks (dacite lavas, pyroclastic rocks of dacite–rhyolite compositions and pumice) associated with sulfide veining and patches/veins of anhydrite. No massive sulfide was found, however, and the subsea‐floor mineralization to 10 m depth is dominated by anhydrite and clay minerals with some sulfides. Sulfide‐bearing samples contained high Au (up to 42 ppm), Ag (up to 263 ppm), As (up to 1550 ppm), Hg (up to 55 ppm), Sb (up to 772 ppm), and Se (up to 24 ppm). Electron probe microanalyzer indicated that realgar, orpiment, and mimetite were major As‐bearing minerals. The sulfides were also characterized by high Zn (>10%) compared to Cu (<6.3%) and Pb (<0.6%). The δ202Hg/198Hg, δ202Hg/199Hg and δ202Hg/200Hg of the sulfide‐bearing dacite samples and a sulfide chimney decreased with increasing Hg/Zn concentration ratio. The variation of the δ202Hg/198Hg ranged from ?2.8 to +0.5‰ to relative to S‐HG02027. The large range of these δ202Hg/198Hg was greater than might be expected for such a heavy element and may be due to a predominance of kinetic effects. The variation of δ202Hg/198Hg of sulfide‐bearing dacite samples suggested that light Hg isotope in the vapor mixed with oxygenated seawater near sea floor during mineralization. Lead isotope ratios of the sulfide were very similar to those of the dacite lava, suggesting that lead is of magmatic origin. The 87Sr/86Sr ratio (0.70872) of anhydrite was different from that of the dacite lava, and suggests an Sr derivation predominantly from seawater. Hydrothermal alteration of the dacite in the Suiyo hydrothermal field was characterized by Fe‐sulfides, anhydrite, barite, montmorillonite, chlorite/montmorillonite mixed‐layer minerals, mica, and chlorite with little or no feldspar or cristobalite. Hydrothermal clay minerals changed with depth from montmorillonite to chlorite/montmorillonite mixed‐layer minerals to chlorite and mica. Hydrogen isotope ratios of chlorite/montmorillonite and mixed‐layer, mica‐chlorite composites obtained below the active venting sites ranged from ?49 to ?24‰, suggesting seawater as the dominant fluid causing alteration. Oxygen isotope ratios of anhydrite ranged from 9.2 to 10.4‰ and anhydrite formation temperatures were calculated to be 188–207°C. Oxygen isotope ratios ranged from +5.2 to +9.2‰ for montmorillonite, +3.2 to +4.5‰ for chlorite/montmorillonite mixed‐layer minerals, and +2.8 to +3.8‰ in mixtures of chlorite and mica. The formation temperatures of montmorillonite and of the chlorite–mica mixture were 160–250°C and 230–270°C, respectively. The isotope temperatures for clay minerals (220–270°C) and anhydrite (188°C) were significantly lower than the borehole temperature (308.3°C) measured just after the drilling, suggesting that temperature at this site is now higher than when clay minerals and anhydrite were formed.  相似文献   

16.
The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO2‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv., 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO2‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H2O, with some CO2 and very little CH4, N2, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ18OH2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ18OH2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ18OH2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ34S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO2 or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO2 from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.  相似文献   

17.
Mercury vapor (Hg0) emission from plants contributes to the atmospheric Hg cycle. Young barley (Hordeum vulgare L.) plants grown on a hydroponic cultivation medium containing Hg(II) have previously been shown to increase their Hg0 emission significantly by reduction of Hg(II) with endogenous ascorbic acid. Regarding the potential contribution to the Hg cycle from the vast forest-covered areas, it was important to investigate this mechanism in trees. The increase in Hg0 emission from young European beech plants cultivated on a HgCl2 medium exceeded that from controls by ca. tenfold and was proportional to the Hg(II) concentration. From these experiments, a flux of 12.8 μg Hg0/h/m2 was estimated at an exposure of the roots to 20 μM Hg(II). Mercury vapor release from homogenates of Norway spruce needles exceeded that from European beech leaves by a factor of 2.3–4, i.e. in proportion to the reported AA concentrations; the reduction was maximal at alkaline pH which is typical for AA. The 8.4-fold difference in Hg0 release between homogenates from wild-type Arabidopsis thaliana and from its AA-deficient mutant vtc 1-1 also paralleled the reported difference in AA levels of both species. It is concluded that the phytoreduction and vaporization of Hg by AA is an important mechanism as much for Hg detoxification in trees as for Hg emission to the atmosphere. The efficiency of this process seems to result from the optimal coordination of transfer and biochemical transformation of mercuric ions and Hg vapor. There is no evidence for a relevant difference in the mechanisms of biogenic Hg(II) reduction between grass plants and trees.  相似文献   

18.
The Don Sixto mining area in Mendoza province, central‐western Argentina, contains an epithermal low sulfidation Au–Ag deposit. It is a small deposit (~4 km2), with a gold resource of 36 t. In Don Sixto, ore minerals are disseminated in the hydrothermal quartz veins and hydrothermally altered volcanic‐pyroclastic rock units of Permian–Triassic age. On the basis of the texture, ore mineral paragenesis and cross cutting relationship of gangue minerals, seven stages of mineralization were recognized and described. The first six stages are characterized by quartz veins with minor amounts of base metal minerals and the last stage is represented by fluorite veins with minimal quantities of base metal minerals; the precious metal mineralization is mainly related to the fourth stage. The hydrothermal veins exhibit mainly massive, crustiform and comb infilling textures; the presence of bladed quartz replacement textures and quartz veins with adularia crystals are indicative of boiling processes in the system. Fluid inclusion and complementary stable isotope studies were performed in quartz, fluorite, and pyrite samples from the vein systems. The microthermometric data were obtained from primary, biphasic (liquid‐vapor) fluid inclusion assemblages in quartz and fluorite. The maximum values for salinity and homogenization temperature (Th) came from the stage IV where quartz with petrographic evidence of boiling has average values of 4.96 wt% NaClequiv. and 286.9°C respectively. The lower values are related to the last stage of mineralization, where the fluid inclusions in fluorite have average salinities of 1.05 wt% NaClequiv. and average homogenization temperatures of 173.1°C. The oxygen and sulfur isotopic fractionation was analyzed in quartz and pyrite. The calculated isotopic fractionation for oxygen in the hydrothermal fluid is in the range of δ18OH2O = ?6.92 up to ?3.08‰, which indicates dominance of a meteoric source for the water, while sulfur reaches δ34SH2S = 1.09‰, which could be reflecting a possible magmatic, or even a mixed source.  相似文献   

19.
Zhuo  Yuzhou  Huang  Yong  Li  Jinwei  Gao  Wei  Li  Jinxiang 《中国地球化学学报》2019,38(5):670-682

Mercury mines in Guizhou province are the main base of mercury production and the most important resource base in China. The San-Dan mercury belt in Guizhou province contains a series of important mercury deposits. However, the source of metallogenic materials and the properties of metallogenic fluid of these mercury deposits have long been a controversial issue. In this study, we used cathode luminescence techniques to distinguish different stages of dolomite and calcite, laser ablation inductively coupled plasma mass spectrometry to analyze the trace elements, and stable isotope mass spectrometry techniques to analyze C–O isotopes compositions of dolomite and calcite in the Sixiangchang mercury deposit in San-Dan mercury belt. We also measured the sulfur isotope composition of cinnabar. Our study showed that dolomite can be divided into two stages, the lumpy dolomite associated with cinnabar in Dol 1 stage and dolomite vein in Dol 2 stage, which is associated with Cal 2 stage calcite vein. With the progress of mineralization, Al, As, Mo, Sb, and Sr elements were gradually enriched in the ore-forming fluid. The rare earth element (REE) partition curve of Dol 1 stage dolomite showed a trend of light REE enrichment. Cal 2 stage calcite and Dol 2 stage dolomite exhibited a flat-type REE partition curve, and Dol 2 stage dolomite showed a strong negative anomaly for Eu. δ13C of carbonate mineral variation ranges from − 6.89 to − 2.16 ‰, while δ18O variation ranges from 13.80 to 23.09 ‰, and the δ34S variation range of cinnabar is 16.51–24.28 ‰. Carbonate mineral trace elements and C–O isotopes compositions suggested that early ore-forming fluid was reduced, and late ore-forming fluid was oxidized. The ore-forming fluid of the Sixiangchang mercury deposit is a mixture of deep crustal fluid and meteoric water in deep thermal circulation, and involved in the oxidation of organic matter. The cinnabar δ34S results showed that sulfur mainly came from seawater sulfate with the participation of microbial reduction. Sulfur is sedimentary in origin and was derived mainly from the host-rock strata.

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20.
The Fengjia barite–fluorite deposit in southeast Sichuan is a stratabound ore deposit which occurs mainly in Lower Ordovician carbonate rocks. Here we present results from fluid inclusion and oxygen and hydrogen isotope studies to determine the nature and origin of the hydrothermal fluids that generated the deposit. The temperature of the ore‐forming fluid shows a range of 86 to 302 °C. Our detailed microthermometric data show that the temperature during mineralization of the fluorite and barite in the early ore‐forming stage was higher than that during the formation of the calcite in the late ore‐forming stage. The salinity varied substantially from 0.18% to 21.19% NaCl eqv., whereas the density was around 1.00 g/cm3. The fluid composition was mainly H2O (>91.33%), followed by CO2, CH4 and traces of C2H6, CO, Ar, and H2S. The dominant cation was Na+ and the dominant anion Cl, followed by Ca2+, SO42‐, K+, and Mg2+, indicating a mid–low‐temperature, mid‐low‐salinity, low‐density NaCl–H2O system. Our results demonstrate that the temperature decreased during the ore‐forming process and the fluid system changed from a closed reducing environment to an open oxidizing environment. The hydrogen and oxygen isotope data demonstrate that the hydrothermal fluids in the study area had multiple sources, primarily formation water, as well as meteoric water and metamorphic water. Combined with the geological setting and mineralization features we infer that the stratabound barite–fluorite deposits originated from mid–low‐temperature hydrothermal fluids and formed vein filling in the fault zone.  相似文献   

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