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1.
The Sailauf MnFeAs vein mineralization, located in the Spessart district (central Germany), is characterized by complex hydrothermal carbonate and oxide assemblages. The mineralization is hosted by a Permian rhyolite body and is structurally related to the Variscan unconformity that separates Permian sedimentary rocks from the underlying Variscan crystalline basement. The hydrothermal vein system has been studied by optical microscopy, electron-microprobe and LA-ICPMS analysis of major and trace elements (including the REE). Four distinct mineralization stages that are characterized by diagnostic carbonate-oxide assemblages are identified, which are (1) pre-ore stage, (2) ore stage 1, (3) ore stage 2, and (4) the replacement stage. Hydrothermal carbonates show complex compositional trends in CaMn (Fe + Mg) space, and comprise calcite, Mn-calcite, FeMg calcite, Ca-rhodochrosite, and Ca-kutnahorite. Oxide assemblages are dominated by braunite and hematite, with minor amounts of manganite and hausmannite. The mineralization is enriched in a distinct suite of trace elements, including As, W, Pb, Zn and Cu. Analysis of the paragenetic evolution, in conjunction with the major and trace element data, allows to reconstruct the fluid evolution of the hydrothermal system. The first order change in mineralogy between the two main ore stages (Mn oxides and calcite evolving into hematite and Mn-rich calcite) records a pronounced shift in fluid pH and silica activity of the system. This interpretation is also supported by variations in the behavior of Ce in different carbonate generations. The late stage replacement carbonates relate to destabilization of the primary ore assemblages. The distinct geological setting immediately below the Permian unconformity, in conjunction with the mineralogical and chemical data, suggests that dynamic fluid mixing processes involving basement-derived brines and more shallow groundwaters were important in the formation of the Sailauf MnFeAs mineralization. The significant enrichment in the AsWPbZnCu element suite resembles that of other MnFe deposits, and points to felsic lithologies as the main metal source of the mineralization.  相似文献   

2.
Although the sources of the ore metals remain problematic in most Iron-oxide Cu and Au (IOCG) deposits, external sulphur, either from surficial basinal brines and seawater (e.g., Central Andean and Carajás deposits) or from formation water and metamorphic fluids (e.g., the Cloncurry deposits), or introduced by magmatic assimilation of metasedimentary units (e.g., Phalaborwa), has been documented in many major Cu-rich IOCG centres. However, only the evaporite-sourced fluids yield diagnostically high δ34S values (i.e., > 10‰), while sedimentary formation water or metamorphic fluids commonly have lower values and are less clearly distinguishable from magmatic fluids, as in the Cloncurry deposits in which the involvement of external fluids is revealed by other evidence, such as noble gas isotopes. On the basis of these arguments, IOCG deposits could be redefined as a clan of Cu (AuAgU) deposits containing abundant hypogene iron oxide (magnetite and/or hematite), in which externally-derived sulphur probably plays an important role for the Cu (AuAgU) mineralization. In this definition, all “Kiruna-type” magnetite deposits, hydrothermal iron deposits (e.g., skarn Fe deposits) and magnetite-rich porphyry CuAu and skarn CuAu deposits are excluded. Two subtypes of IOCG deposits are recognized on the basis of the predominant iron oxide directly associated with the Cu (Au) mineralization, whether magnetite or hematite. Neither magnetite- nor hematite-rich IOCG deposits show any preference for specific host rocks, and both range in age from Neoarchean to Pleistocene, within a broad tectonic environment.  相似文献   

3.
Although garnet UPb dating method has been reported recently, yet the accurate concordia 206Pb/238U ages and growth histories of multi generation of garnets based on ages were still lacked. LA-ICP-MS UPb dating on multi-generational grandite (grossular-andradite) garnet from the large Tonglvshan Cu-Fe-Au skarn deposit was applied in this study. Based on petrographic observation, in chronological order, three generation garnets have been distinguished, namely homogeneous Grt1-exo (in the exoskarn zone) and Grt1-endo (in the endoskarn zone), oscillatory zoning Grt2 and vein-type Grt3 cutting magnetite ores. LA-ICP-MS UPb dating on four grandite samples from the Grt1-exo, Grt1-edno, Grt2 and Grt3 yields Tera-Wasserburg lower intercept 206Pb/238U ages of 139.1 ± 1.0 Ma (2σ, MSWD = 0.79), 134 ± 11 Ma (2σ, MSWD = 2.5), 143.4 ± 8.3 Ma (2σ, MSWD = 2.3) and 140.3 ± 1.4 Ma (2σ, MSWD = 0.95), respectively. More importantly, two concordia 206Pb/238U ages of 139.2 ± 0.6 Ma (2σ, MSWD = 1.4) and 139.8 ± 1.5 Ma (2σ, MSWD = 0.13) were firstly obtained from the sample of Grt1-exo with highest U concentrations ([U]avg > 80 ppm) contents. The precision UPb ages of 139–140 Ma from Grt1-exo and Grt3 can be considered as the timing of Cu-Fe-Au skarn mineralization, and consistent with the majority of published zircon UPb ages of the quartz dioritic stock and 40Ar39Ar plateau ages of phlogopite at Tonglvshan (142–140 Ma). The precision grandite UPb ages also indicate that the entire metasomatic hydrothermal mineralization activity in the Tonglvshan Cu-Fe-Au skarn deposit occurred within a relatively short time span of <1 (or 2.5 considering errors) Myr. In addition, we found that the grandite garnet is more easily to be enriched in U and can obtain the high-precision concordia UPb ages with higher andradite Mol%, euhedral and larger crystals, and relevant oxidized magmatic rocks or skarns.  相似文献   

4.
Geochemical, SrNd isotopic and geochronological methods were used to reveal the protoliths and geodynamic implications of the newly discovered Triassic Baqing eclogites, eastern Qiangtang terrane, central Tibet. We assessed the mobility of trace elements, and it turned out that high field strength elements (HFSEs) and rare earth elements (REEs) were immobile in the high-pressure (HP) metamorphic process and reliably employed to discriminate the protoliths of the Baqing eclogites. Whole-rock geochemical data (especially immobile elements) suggested both arc-related (negative NbTa anomalies, high light (L) REEs/heavy (H) REEs ratios) and mid-oceanic ridge basalt (MORB)-related (without negative NbTa anomalies, relatively low REEs contents) characteristics, indicating the contribution of different proportions of subduction material with a backarc basin origin. According to the SrNd isotopic ratios (initial 87Sr/86Sr ratios: 0.7078–0.7086; εNd(t) values: −0.58 to +1.96), the protoliths of the Baqing eclogites originated from mantle which experienced continental crustal contamination in the subduction zone. Compared with nearby subduction-related magmatic rocks from eastern Qiangtang terrane, backarc basin was the most likely tectonic environment for the Baqing eclogite protoliths. The Jinsha Paleo-Tethyan Ocean southward subduction underneath East Qiangtang block (EQB) and rollback led to the formation of this backarc basin between the Late Permian and Early Triassic, and subsequent northward subduction of the backarc basin formed the Baqing eclogites in early Late Triassic (227–221 Ma).  相似文献   

5.
《Comptes Rendus Geoscience》2014,346(11-12):317-325
Major features of the Earth's structure and dynamics originate in the contrast between the rigidity of SiO bonds and the softness of SiOSi linkages. Because this contrast results from orbital hybridization, a real understanding of bonding relies on ab initio quantum-mechanical principles. As investigated with first-principles interatomic potentials, the α–β transitions of SiO2 polymorphs illustrate how soft SiOSi linkages give rise to dynamical structures at rather low temperatures and yield the low melting temperatures of SiO2-rich minerals that are at the roots of SiO2 enrichment in magmatic differentiation. The increasing concentration of alkalis throughout this process is another aspect that must also be studied in terms of molecular orbitals in relation with the presence of aluminum in tetrahedral coordination. Finally, calculations of noble gas solubility show that some important features can be treated with “hybrid” calculations when, in addition to quantum-mechanical effects, the energy needed to create a cavity in the silicate melt is dealt with in a classical manner.  相似文献   

6.
《Gondwana Research》2013,23(3-4):799-809
Externally derived, pure CO2 that mixes with a carbon-(under)saturated C-O-H fluid in lower crustal granulites may result in graphite precipitation if the host-rock oxygen fugacity (fO2rock) is below the upper fO2 limit of graphite. The maximum relative amount of graphite that can precipitate varies between a few mol% up to more than 25 mol%, depending on pressure, temperature, and host-rock redox state. The maximum relative amount of graphite that can precipitate from an infiltrating CO2 fluid into a dry granulite (CO fluid system) varies between zero and a few mol%. Thermodynamic evaluation of the graphite precipitation process shows that CO2 infiltration into lower crustal rocks does not always result in a carbon (super)saturated fluid. In that case, graphite precipitation is only possible if carbon saturation can be reached as a result of the reaction CO2  CO + ½ O2. Graphite that has been precipitated during granulite facies metamorphic conditions can subsequently be absorbed by a COH fluid during retrograde metamorphism. It is also possible, however, that significant amounts of graphite precipitate from a COH fluid during retrograde metamorphism. This study shows that interpreting the presence or absence of graphite in granulites with respect to CO2 infiltration requires detailed information on the PTfO2rock conditions, the relative amount of CO2 that infiltrates into the rock, and whether H2O is present or not.  相似文献   

7.
The Zapug–Duobuza magmatic arc (ZDMA), located along the southern edge of the south Qiangtang terrane in western Tibet, extends east–west for ~ 400 km. Small scattered granite and porphyry intrusions crop out in the ZDMA, but a large amount of granite may be buried by Late Cretaceous to Paleogene thrusting. Two stages of magmatism have been identified, at 170–150 Ma and 130–110 Ma. The widely distributed Middle–Late Jurassic granite intrusions in the ZDMA exhibit SrNd isotopic characteristics similar to those of ore-bearing porphyries in the Duolong giant CuAu deposit, and their εHf(t) values mostly overlap those of other porphyry CuMo deposits in the ZDMA and the Gangdese zone. The SrNdHf isotopic geochemistry suggests variable contributions of mantle and Qiangtang crustal sources, and indicates the presence of two new ore districts with potentials for CuAu, Fe, and PbZn ores, located in the Jiacuo–Liqunshan and Larelaxin–Caima areas. Except for the Duolong ore-forming porphyries, which show significant contributions of mantle components intruded into an accretionary mélange setting, the Early Cretaceous granites in other areas of the belt are of mostly crustal origin, from sources in Qiangtang felsic basement and Permo-Carboniferous strata, indicating the weak ore-forming potential of skarn-type Fe and PbZn deposits. The ephemeral but deep Bangong Co–Nujiang ocean in the Early Jurassic evolved into a shallow compressional marine basin in the Middle–Late Jurassic, possibly transitioning to northward flat subduction of oceanic crust at this time. The subducted slab broke off in the Early Cretaceous, initiating a peak in arc magmatism and metallogenesis at 125–110 Ma.  相似文献   

8.
Isotopes (RbSr, C, O, S, and Pb) were investigated from the Zhenzigou PbZn deposit in the Qingchengzi mineral field (QMF) of the North China Craton as an aid to determine the genesis of stratiform PbZn deposits in the Liao-Ji Rift. A step-dissolution RbSr age of 1798 ± 8 Ma with 206Pb/204Pb ratios of 17.7477–17.8527 were obtained from sphalerite. Sulfur isotopic ratios for pyrite (5–14.4‰), sphalerite (2.4–8.6‰), and galena (− 0.3–8.6‰) from Zhenzigou have a narrower range than those from the host Paleoproterozoic Dashiqiao Formation, and granite in the area. Calcite and limestone from ore and wallrocks at the deposit have similar C and O isotope compositions, with δ13CPDB ranging from − 6.0 to − 2.3‰ and δ18OSMOW from 9.8 to 13.7‰, which are similar to those of carbonatite and the mantle.Comprehensive analysis of the Pb isotopic composition of the sulfide from the Zhenzigou deposit and PbZn deposits in adjacent area show that the Pb originated from the upper crust and mixed with Pb from the mantle. Sulfur isotopes from Zhenzigou deposit indicate that the mineralization has a volcanic eruption source. The δ13CPDB and δ18OSMOW values indicate that the CO2 originated from a mixed mantle, marine carbonate and organic source.Combined with the study of regional metallogenic background, this paper proposes that deposition of stratiform PbZn mineralization in the QMF began ca. 2052 Ma during development of the Liaoji Rift. The mineralization extended to ca. 1798 Ma prior to deformation associated with the Lvliang Movement, which dismembered the stratiform PbZn mineralization. The veined mineralization in the region cross-cuts the stratiform deposits and represents remobilized and redeposited deposits associated with the emplacement of Triassic plutons such as the Xinling and Shuangdinggou granites.  相似文献   

9.
SmNd, RbSr and ThUPb zircon ages for four syn-tectonic and two post-tectonic granitoids from the Axum area of northern Ethiopia are determined. Two of the syn-tectonic granitoids (the Azeho and Deset) are intrusions into structurally southeast facing, predominantly tholeiitic arc metavolcanics and associated metasediments situated west of the central steep zone in the area. The other two syn-tectonic granitoids (the Chila and Rama) are intrusions into structurally northwest facing metasediments and calc-alkaline metavolcanics at the eastern part of the steep zone. One of the post-tectonic granites (the Sibta Granite) occurs west of the central steep zone and the second (the Shire Granite) cuts the central steep zone. Preliminary geochemical data of all the granitoids show that they are enriched in large ion lithophile elements, depleted in high field strength elements and have 1-type characteristics, similar to calc-alkaline granitoids in subduction-related volcanic arc setting. The geochronological data indicate three discrete intrusive events: ∼800 Ma to the east of the central steep zone, ∼750 Ma to the west and a post-tectonic intrusion at around 550 Ma. The ∼-750 and ∼800 Ma ages of the intrusives are interpreted as minimum ages of arc magmatism in the respective blocks across the central steep zone, and the ∼550 Ma age of the post-tectonic granites records the final magmatic event in the region. The contrast of age across the central steep zone emphasises that this zone is a major structural element that might have played a significant role during the accretion of structurally and lithologically contrasting tectonostratigraphical blocks.  相似文献   

10.
In order to understand and mitigate the deterioration of water quality in the aquifer system underlying Guadalajara metropolitan area, an investigation was performed developing geochemical evolution models for assessment of groundwater chemical processes. The models helped not only to conceptualize the groundwater geochemistry, but also to evaluate the relative influence of anthropogenic inputs and natural sources of salinity to the groundwater. Mixing processes, ion exchange, water–rock–water interactions and nitrate pollution and denitrification were identified and confirmed using mass-balance models constraint by information on hydrogeology, groundwater chemistry, lithology and stability of geochemical phases. The water–rock interactions in the volcanic setting produced a dominant NaHCO3 water type, followed by NaMgCaHCO3 and NaCaHCO3. For geochemical evolution modeling, flow sections were selected representing recharge and non-recharge processes and a variety of mixing conditions. Recharge processes are dominated by dissolution of soil CO2 gas, calcite, gypsum, albite and biotite, and Ca/Na exchange. Non-recharge processes show that the production of carbonic acid and Ca/Na exchange are decreasing, while other minerals such as halite and amorphous SiO2 are precipitated. The origin of nitrate pollution in groundwater are fertilizers in rural plots and wastewater and waste disposal in the urban area. This investigation may help water authorities to adequately address and manage groundwater contamination.  相似文献   

11.
《Applied Geochemistry》1993,8(1):81-100
Detailed chemical and isotope analysis of 87 formation waters collected from six Devonian-aged units in the Michigan Basin are presented and discussed in terms of the origin of the dissolved components and the water. Total dissolved solids in these waters range from 200,000 to >400,000mg/1. Upper Devonian formations produce dominantly NaCaCl brine, while deeper formations produce CaNaCl water. Ratios of Cl/Br and Na/Br along with divalent cation content (MCl2), indicate that these brines are derived from evapo-concentrated seawater. Other ion concentrations appear to be extensively modified from seawater values by water-rock reactions. The most important reactions are dolomitization, which explains the Ca content of the brines, and reactions involving aluminosilicate minerals. Stable isotope (δ18O and δD) compositions indicate that water molecules in the deeper formations are derived from primary concentrated seawater. Isotope enrichment by exchange with carbonates and perhaps gypsum cannot be discounted. Isotope values indicate water in the Upper Devonian formations is a mixture of seawater brine diluted with meteoric-derived water. Dilution has predominantly occurred in basin margins. Two scenarios are presented for the origin of the brines in the Devonian formations: (1) they originated when the Devonian sediments and evaporites were first deposited; or (2) they are residual brine liberated from the deeper Devonian and possibly Silurian salt deposits.  相似文献   

12.
Stable Zn isotopes may be applied to trace the source of ore-forming metals in various types of PbZn deposits. To test this application, Zn and Pb isotope systematics for sulfides and associated basement rocks as well as FeMn carbonates (gangue) from the Zhaxikang PbZn deposit in South Tibet have been analyzed. The basement in this region includes metamorphosed mafic to felsic rocks (dolerite, quartz diorite, rhyolite porphyry, pyroclastics and porphyritic monzogranite). These rocks have similar δ66Zn values of 0.33 to 0.37‰, with an average value of 0.36 ± 0.03‰ (2σ), except for the more evolved porphyritic monzogranite that has a heavier value of 0.49‰. FeMn carbonates are present as hydrothermal veins and were probably precipitated from magmatic fluids. They have an average δ66Zn value of 0.27 ± 0.05‰, which is slightly lighter than the basement rocks, possibly representing δ66Zn isotopic compositions of the hydrothermal fluids. Sphalerite and galena have similar Zn isotopic compositions with δ66Zn ranging from 0.03 to 0.26‰ and 0.21 to 0.28‰, respectively. Considering the Zn isotope fractionation factor between sphalerite and fluids of − 0.2‰ at ~ 300 °C as reported in literature, hydrothermal fluids from which these sulfides precipitated will have δ66Zn values of ca. 0.39 ± 0.10‰, which are consistent with the values of basement rocks and the FeMn carbonates. This similarity supports a magmatic-hydrothermal origin of the Zhaxikang PbZn deposit. Both Pb and S isotopes in these sphalerite and galena show large variations and are consistent with being derived from a mixture of basement and sedimentary rocks in various proportions. Zn isotopic compositions of the sulfides significantly extend the range of regional basement rocks, suggesting that sedimentary rocks (e.g., shales) are also a significant source of Zn. However, the Zn isotopic compositions of sphalerite and galena differ from those of marine carbonates and those of typical SEDEX-type deposits (e.g. Kelley et al., 2009), confirming a magmatic-hydrothermal model. Combined with regional geological observations and the age constraints of ~ 20 Ma (Zheng et al., 2012, 2014), the results of our investigation indicate that the Zhaxikang PbZn deposit is most likely a magmatic-hydrothermal deposit.  相似文献   

13.
Direct dating of W and WSn deposits by wolframite is more reliable relatively to gangue mineral and important for understanding their timing and genesis. However, such analysis still lacks of homogeneous wolframite standard recently. Due to containing considerable and variable common lead, and inhomogeneous in different grains, the wolframite sample of MTM, which is a promising candidate reference material proposed by previous studies, is not suitable as a primary standard for wolframite UPb dating by LA-ICP-MS using the normal normalization method as zircons. In this contribution, a modified normalization method is established for wolframite UPb dating, in which NIST612 or 614 and MTM are used for correction of PbPb and UPb ratios, respectively. Wolframite UPb dating are performed on the Langcun, Xihuashan, Piaotang, Shamai W or WSn deposits and the Baiganhu ore district, the obtained lower intercept 206Pb/238U ages are comparable with the ages from syngenetic molybdenite, cassiterite, muscovite and the genetically related granites, as well as wolframite by water vapor-assisted ns-LA-ICP-MS UPb dating method. The results of this analysis demonstrate that the robust age for W mineralization can be determined by LA-ICP-MS UPb dating of wolframite using this modified calibration method. Mineralization ages of 125–130 Ma by directly dating of metal minerals for the Langcun W, Jianfengpo Sn and large-size Xianglushan W deposits confirm that there exists an important WSn mineralization event in this period. The close temporal and spatial correlation indicates the granites and W-Cu-Mo-Pb-Zn-Sn mineralization have a genetic relationship with each other and are resulted from the same tectonic-magmatic-hydrothermal events during 140 to 120 Ma in South China.  相似文献   

14.
The petrogenesis and tectonic evolution of the Mesozoic ophiolitic mélanges in the western section of the Yarlung Zangbo suture zone (YZSZ) remain controversial. In this paper, we present the results of whole-rock geochemical and SrNd isotope analyses, zircon UPb ages and in situ LuHf isotopic data obtained from mafic rocks of the northern and southern sub-belts of the western YZSZ Mesozoic ophiolitic mélanges to help us understand these controversial issues. Diabases and dolerites from the northern sub-belt and gabbros from the southern sub-belt exhibit variable fore-arc basalt (FAB)-like geochemical compositions and have zircon UPb ages of ∼126.4–120.3 Ma. In addition, gabbro-diabases from the northern sub-belt have boninite series affinities and yield a zircon UPb age of ∼125.7 Ma. These results, along with previous studies on the YZSZ Mesozoic ophiolitic mélanges and the Gangdese arc, reveal that the western YZSZ Mesozoic ophiolites were likely generated over multiple stages in the epicontinental Gangdese fore-arc basin as the Yarlung Zangbo Neo-Tethyan Ocean subducted northward in front of the Lhasa terrane. The Early Cretaceous FAB-like and boninite series mafic rocks were formed by the reinitiation of subduction, which was followed by a retreat of the subduction zone and the creation of the fore-arc basin and strong hyperextension, accompanied by asthenosphere upwelling at ∼130–120 Ma. During this process, the upwelling asthenosphere underwent decompressional melting with limited penetration of slab-derived fluids and gave rise to the N-MORB (normal mid-ocean ridge basalt)-like basaltic magmas that intruded the overlying, previously generated depleted mantle as FAB-like gabbro, diabase and dolerite sills or dykes. Then, boninitic magmas represented by boninitic gabbro-diabases were generated by remelting the extremely depleted residual mantle source, which was metasomatized by a small amount of slab-derived fluids, following previous extractions of FAB-like magma.  相似文献   

15.
《Applied Geochemistry》1996,11(4):541-554
In the acidic stream (pH 2.2–4) of the Carnoulès Pb-(Zn) mine, Gard, France, very high As contents (from 9 to 20%) can be accumulated as ferric arsenate and arsenate-sulphate precipitates in rapidly growing bacteria-made structures. The main bacterial forms are rod-shaped and sheathed, their sheath is made of Fe-As-rich material and is coated with ferric arsenate colloidal particles or may be partially included in authigenic crystals. Living forms ofThiobacillus-type bacteria have been recognized in the precipitates. The cyclic development of bacterial colonies alternating with sand deposition and erosive episodes results in the formation of As-rich ferruginous accretions. These laminated and dome-shaped bacterial constructions are similar to those of stromatolites. The extremely high contents of solute As in upstream flow (250 mg/1) are lowered by 2–3 order of magnitude downstream. Lead is also precipitated and concentrated in this FeAs-rich bacterial stromatolite (2500 ppm Pb). This accumulation and concentration of As and heavy metals via direct or induced microbial action limits pollution downflow. But seasonal storms could erode these FeAsPb-rich deposits and drastically increase pollution.The accumulation of ferric arsenate by bacterial stromatolites suggests that possible microbial remediation strategies may be used in acid mine drainage environments.  相似文献   

16.
Two generations of primary olivine are present in kimberlite, rounded phenocrysts (Fo94Fo91) and euhedral groundmass olivines (Fo91Fo88-5). Rounded phenocrysts less magnesian than Fo88 are considered to be mantle derived xenocrysts; such crystals comprise up to 40% of the phenocrysts material in kimberlite. Calculated silica activity ranges from 10?1,5 at 1200 °C, 50 kbs, to between 10?1,6 and 10?2.4 at 600 °C, 0.5–1.0 kb. Silica buffers involving olivines, pyroxenes and garnet are considered. Oxygen fugacities on the order of 10?20 bars indicate that kimberlite magmas are highly reduced at the time of groundmass formation.  相似文献   

17.
《Applied Geochemistry》1994,9(6):609-626
The Saint-Salvy vein-hosted Zn (+Ge) deposit occurs in an E–W fault system which flanks the southern margin of the late Variscan Sidobre granite, and cross-cuts Cambrian black shales of the Palaeozoic basement. Comprehensive mineralogical and geochemical studies of vein samples have revealed four mineralizing events (M1–M4) related to late and post-Variscan tectonic events. A further late-stage event may be related to weathering.M1 (=skarn deposits) and M2 (=patchily mineralized quartz veinlets) are associated with granite emplacement. Quartz contains low salinity, H2OCO2(NaCl)-dominated fluids(⩽6wt% NaCl equiv.) of relatively high temperature (300–580°C), trapped under moderate to high pressure. Estimated M1 fluid δD and calculated fluidδ18O plot within the metamorphic water field. There appears to be no involvement of magmatic fluids.By contrast, M3 (= barren quartz) and M4 (= zinciferous economic mineralization) stages have H2OCO2NaClCaCl2 fluid inclusions with high salinities (23–25 wt% NaCl equiv.) and low temperatures(∼ 80–140°C), which were trapped under low-pressure conditions. The high salinity and NaCl + CaCl2 content of both M3 and M4 indicates that their parent fluids leached evaporitic salts. M3 fluids are meteoric water dominated, falling close to the meteoric water line (δD andδ18O averaging −64 and −8‰, respectively). M4 fluids have highly distinctive δD averaging −101‰, and calculated fluidδ18O varying from−1.2to+7.1‰. The unusually low δD composition of M4 suggests the involvement of “organic” fluids, in which H is derived directly or indirectly from organic matter. The relatively highδ18O of M4 fluids indicates that considerable isotopic exchange with sedimentary material took place, displacing theδ18O from the meteoric water line. The data imply interaction of meteoric waters with evaporite and hydrocarbon-bearing sedimentary sequences, most probably the adjacent Aquitain Basin.The main economic mineralization (M4 stage) took place during a tensional event, probably coincident with the Lias-Dogger transition.Calculatedδ34SH2S of M4 sulphide(+5.4to+8.2‰) is almost identical toδ34S of local Cambrian sulphides(+4.7to+9.4‰) suggesting a genetic link. Abundant siderite associated with M4 sphalerite hasδ13C ranging from−2.6to−4.4‰ indicating that carbon was sourced from sedimentary carbonate mobilized by, or equilibrated with the hydrothermal fluid.Late-stage sulphides exhibit extraordinary and highly distinctiveδ34S. Sphalerite has extremely low δ34S(−42.5to−50.5‰), whereas pyrite has an extraordinary large range from−33.2‰to+74.3‰. Closed system sulphate reduction is held to be responsible for the extremely highδ34S: whereas more open system reduction produces the very low values. The coincidence of isotopically lowδ13C(−7.6to−11.9‰) for co-genetic calcite suggests the involvement of organic matter in the reduction process.  相似文献   

18.
The giant Yulong porphyry CuMo deposit was formed in postsubduction setting in eastern Tibet. Origin of the ore-related Yulong intrusion remains a matter of debate. This study presents new whole-rock major and trace element geochemistry, in-situ apatite SrNd and zircon HfO isotopes, and mineralogical chemistry of the Yulong intrusion. Least-altered samples from the Yulong intrusion have high SiO2 (66.3–69.5 wt%) and Al2O3 (14.9–15.5 wt%) contents, high La/Yb (36.4–68.0) and Sr/Y (46.0–76.3) ratios, and low MgO (0.63–1.24 wt%) and Cr (<30 ppm) contents, similar to adakitic rocks deriving from thick juvenile lower crust. They are enriched in large ion lithophile elements (LILEs) and depletion in high field strength elements (HFSEs), and show listric REE patterns. In-situ apatite SrNd isotopes show limited variations ((87Sr/86Sr)i = 0.7060–0.7068, εNd(t) = −4.8–0.2), which plot between Paleo-Tethys ocean-related arc magmas and the ancient crust in eastern Tibet. Zircon grains from this study and published studies have mostly positive yet variable εHf(t) values (−20.6 to +12.2) and young Hf model ages that overlap those of the Paleo-Tethys ocean-related arc magmas. The above Sr-Nd-Hf isotopes, together with the elevated zircon δ18O values (6.4 to 9.3‰) and arc-like trace element patterns, collectively suggest that the Yulong intrusion may have originated from partial melting of juvenile lower arc crust related to the subduction of the Paleo-Tethys ocean, with incorporation of a small amount of ancient crustal materials.Two generations of amphibole were recognized at Yulong. Their compositions are used to calculate crystallization depths, magmatic oxidation states, and water contents. The caculated results show that the early-stage euhedral high-Al (5.87–8.51 wt%) amphibole phenocrysts may have crystallized in the underlying magma chamber (7.1–12.5 km in depth), whereas the late-stage xenomorphic low-Al (3.47–4.87 wt%) amphibole grains may have crystallized in the porphyritic stock (4.0–5.6 km). Magmatic water contents decrease from early- (3.5–4.6 wt%) to late-stage (2.8–3.5 wt%) amphibole, which is interpreted to indicate fluid exsolution from the magma chamber during emplacement of the Yulong intrusion. Caculated oxidation states increase from early- (ΔNNO = 0.6–1.5) to late-stage (ΔNNO = 1.9–2.3) amphibole. Plagioclase phenocrysts show periodic or reverse core-to-rim zonation of An contents (range up to 25 mol%), which are coupled by FeO contents, probably suggesting magma recharge events. Collectively, we propose that the magma chamber beneath Yulong was recharged by a less evolved magma, and was saturated in fluids to produce intensive alteration and mineralization. The relatively high oxidation states allow the metals to be enriched in the evolving magma, and to be deposited in the hydrothermal alteration stage.  相似文献   

19.
The present paper reports the first detailed petrological and geochemical study of non-sulfide Zn–(FePb) deposits in the Riópar area (Prebetic Zone of the Mesozoic Betic Basin, SE Spain), constraining the origin and evolution of ore-forming fluids. In Riópar both sulfide and non-sulfide Zn–(FePb) (“calamine”) ores are hosted in hydrothermally dolomitized Lower Cretaceous limestones. The hypogene sulfides comprise sphalerite, marcasite and minor galena. Calamine ores consist of Zn-carbonates (smithsonite and scarce hydrozincite), associated with abundant Fe-(hydr)oxides (goethite and hematite) and minor Pb-carbonates (cerussite). Three smithsonite types have been recognized: i) Sm-I consists of brown anhedral microcrystalline aggregates as encrustations replacing sphalerite; ii) Sm-II refers to brownish subhedral aggregates of rugged appearance related with Fe oxi-hydroxides in the surface crystals, which replace extensively sphalerite; and iii) Sm-III smithsonite appears as coarse grayish botryoidal aggregates in microkarstic cavities and porosity. Hydrozincite is scarce and appears as milky white botryoidal encrustations in cavities replacing smithsonite. Also, two types of cerussite have been identified: i) Cer-I cerussite consists of fine crystals replacing galena along cleavage planes and crystal surfaces; and ii) Cer-II conforms fine botryoidal crystals found infill porosity. Calcite and thin gypsum encrustations were also recognized. The field and petrographic observations of the Riópar non-sulfide Zn–(FePb) revealed two successive stages of supergene ore formation under meteoric fluid processes: i) “gossan” and “red calamine” formation in the uppermost parts of the ore with deposition of Fe-(hydr)oxides and Zn- and Pb-carbonates (Sm-I, Sm-II and Cer-I), occurring as direct replacements of ZnPb sulfides; and ii) “gray calamine” ore formation with deposition of Sm-III, Cer-II and hydrozincite infilling microkarst cavities and porosity. The stable isotope variation of Riópar smithsonite is very similar to those obtained in other calamine-ore deposits around the world. Their CO isotope data (δ18O: + 27.8 to + 29.6‰ V-SMOW; δ13C: − 6.3 to + 0.4‰ V-PDB), puts constrains on: i) the oxidizing fluid type, which was of meteoric origin with temperatures of 12 to 19 °C, suggesting a supergene weathering process for the calamine-ore formation under a temperate climate; and ii) the carbon source, that resulted from mixing between two CO2 components derived from: the dissolution of host-dolomite (13C-enriched source) and vegetation decomposition (13C-depleted component).  相似文献   

20.
The age and origin of the past-producing Nanisivik carbonate-hosted ZnPb deposit in Nunavut, Canada, have been controversial for decades. Various direct and indirect dating methods have produced results ranging from Mesoproterozoic to Ordovician in age, and previous studies of the mineralising fluids have suggested that the fluids were anomalously hot (> 150 °C). This study combines ReOs (pyrite) geochronology, in-situ sulphur isotope analysis, and fluid inclusion analysis to refine both the timing of mineralisation and the nature of mineralising fluids. ReOs pyrite analysis shows that the Nanisivik deposit formed ca. 1.1 Ga, broadly similar to the depositional age of the host rock and with the Grenville orogeny, making it one of few known Precambrian carbonate-hosted ZnPb deposits. In-situ sulphur isotope measurements from Nanisivik show a narrow δ34S range of 27.54 ± 0.72, very similar to what has been reported before in bulk sample analyses. New fluid inclusion data show that the mineralising fluids were ~ 100 °C, which is not anomalous in the context of carbonate-hosted base-metal deposits. The fluids exhibit no significant spatial variation in homogenisation temperature in the 2-km-long ‘upper lens’ of the ore deposit, but recrystallisation and modification of fluid inclusions took place in the immediate vicinity of the cross-cutting ~ 720 Ma “mine dyke”. The deposit is broadly inferred to have formed during late Mesoproterozoic assembly of supercontinent Rodinia, when regional hydrostatic head developed under the influence of far-field stresses originating in the developing Grenville orogen. The Nanisivik deposit remains anomalous only in its age; most other aspects of this ore deposit are now shown to be quite typical for carbonate-hosted ore deposits.  相似文献   

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