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1.
Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (Th) up to ∼80 °C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite δ18O values, and depositional timing is constrained by the 207Pb/235U ages of chalcedony or opal in the deposits. Fluid inclusion Th from 50 samples of calcite and four samples of fluorite range from ∼35 to ∼90 °C. Calcite δ18O values range from ∼0 to ∼22‰ (SMOW) but most fall between 12 and 20‰. The highest Th and the lowest δ18O values are found in the older calcite. Calcite Th and δ18O values indicate that most calcite precipitated from water with δ18O values between −13 and −7‰, similar to modern meteoric waters.  相似文献   

2.
In the Schwarzwald area, southwest Germany, more than 400 hydrothermal veins hosting different gangue and ore mineral assemblages cross-cut the crystalline basement rocks. Many of the post-Variscan fluorite-barite-quartz veins are considered to have precipitated through mixing of a deep saline brine with meteoric, low salinity waters. This hypothesis was tested using carbon, sulfur, and oxygen isotope data of sulfides, sulfates and calcite, coupled with fluid inclusion studies. Primary hydrothermal calcites from the deposits show a positive correlation of their δ13C (V-PDB) and δ18O (V-SMOW) values, which range from −12 to −3‰ and from 12 to 18.5‰, respectively. Carbon and oxygen isotope compositions of paragenetically young, remobilized calcite types are shifted towards higher values and range from −12 to −1‰ and from 20 to 25‰, respectively. We developed an improved calculation procedure for modeling the covariation of carbon and oxygen isotopes in calcite resulting from mixing of two fluids with different isotopic compositions and total carbon concentrations. In our model, the carbon speciation in the two model fluid end-members and the fluid mixtures are calculated using a speciation and reaction path code. The carbon and oxygen isotope covariation of primary Schwarzwald calcites can effectively be modeled by a mixing trend of a deep saline brine and a meteoric, low salinity water. Sulfur isotope data of barites from 44 hydrothermal fluorite-barite-quartz veins vary from 9 to 18‰ (CDT), sulfide ore minerals show δ34S values between −14.4 and 2.9‰. Calculated sulfide-sulfate equilibrium temperatures are in the range between 300 and 350 °C. These temperatures differ significantly from the formation temperatures of 150 to 200 °C of most of the deposits as estimated from fluid inclusions, and are interpreted as preserved paleotemperatures of the deep aquifer. This assumption has been carefully checked against possible contamination of an equilibrated sulfide-sulfate system from the deep aquifer with sulfate from surface-derived sources, considering also the kinetics of the sulfide-sulfate isotope exchange. A combination of the S isotopic results with microthermometric fluid inclusion data and constraints on the temperature of the meteoric water was used to calculate mixing ratios of the two fluid end-members. The results indicate that mass fractions of the deep saline brine in the mixed fluid were between 0.5 and 0.75. Considering all geologic, geochemical and isotopic information, we propose that the majority of the post-Variscan hydrothermal veins in the Schwarzwald area were precipitated by district-scale mixing of a homogeneous deep saline brine with meteoric waters.  相似文献   

3.
The Hujiayu Cu deposit,representative of the "HuBi-type" Cu deposits in the Zhongtiao Mountains district in the southern edge of the North China Craton,is primarily hosted in graphitebearing schists and carbonate rocks.The ore minerals comprise mainly chalcopyrite,with minor sphalerite,siegenite[(Co,Ni)_3S_4],and clausthalite[Pb(S,Se)].The gangue minerals are mainly quartz and dolomite,with minor albite.Four fluid inclusion types were recognized in the chalcopyrite-pyrite-dolomite-quartz veins,including CO_2-rich inclusions(type Ⅰ),low-salinity,liquid-dominated,biphase aqueous inclusions(type Ⅱ),solid-bearing aqueous inclusions(type Ⅲ),and solid-bearing aqueous-carbonic inclusions(type Ⅳ).Type I inclusion can be further divided into two sub-types,i.e.,monophase CO_2 inclusions(type Ⅰa) and biphase CO_2-rich inclusions(with a visible aqueous phase),and type Ⅲ inclusion is divided into a subtype with a halite daughter mineral(type Ⅲa) and a subtype with multiple solids(type Ⅲb).Various fluid inclusion assemblages(FIAs) were identified through petrographic observations,and were classified into four groups.The group-1 FIA,consisting of monophase CO_2 inclusions(type Ⅰa),homogenized into the liquid phase in a large range of temperatures from-1 to 28℃,suggesting post-entrapment modification.The group-2 FIA consists of type Ⅰb,Ⅲb and Ⅳ inclusions,and is interpreted to reflect fluid immiscibility.The group-3 FIA comprises type Ⅱ and Ⅲa inclusions,and the group-4FIA consists of type Ⅱ inclusions with consistent phase ratios.The group-1 and group-2 FIAs are interpreted to be entrapped during mineralization,whereas group-3 and group-4 FIAs probably represent the post-mineralization fluids.The solid CO_2 melting temperatures range from-60.6 to56.6℃ and from-66.0 to-63.4℃ for type Ⅰa and type Ⅳ inclusions,respectively.The homogenization temperatures for type Ⅱ inclusions range from 132 to 170℃ for group-3 FIAs and115 to 219℃ for group-4 FIAs.The halite melting temperatures range from 530 to 562℃ for typeⅢ b and Ⅳ inclusions,whereas those for type Ⅲa inclusions range from 198 to 398℃.Laser Raman and SEM-EDS results show that the gas species in fluid inclusions are mainly CO_2 with minor CH_4,and the solids are dominated by calcite and halite.The calcite in the hosting marble and dolomite in the hydrothermal veins have δ~(13)C_(V-pdb) values of-0.2 to 1.2‰ and-1.2 to-6.3‰,and δ~(18)O_(v-smow) values of 14.0 to 20.8 ‰ and 13.2 to 14.3‰,respectively.The fluid inclusion and carbon-oxygen isotope data suggest that the ore-forming fluids were probably derived from metamorphic fluids,which had reacted with organic matter in sedimentary rocks or graphite and undergone phase separation at 1.4-1.8 kbar and 230-240℃,after peak metamorphism.It is proposed that the Hujiayu Cu deposit consists of two mineralization stages.The early stage mineralization,characterized by disseminated and veinlet copper sulfides,probably took place in an environment similar to sediment-hosted stratiform copper mineralization.Ore minerals formed in this precursor mineralization stage were remobilized and enriched in the late metamorphic hydrothermal stage,leading to the formation of thick quartz-dolomite-sulfides veins.  相似文献   

4.
The Ag-Ni-Co-Bi-As-U veins in the Northwest Territories of Canada are hosted by volcano-sedimentary and intrusive rocks of the Great Bear Batholithic Complex. Fluid inclusion data from the gangue minerals of the veins suggest a wide range in salinity and temperature for the hydrothermal fluids. The salinities of the fluids range from about 15 to 35 wt.% NaCl equivalent. The homogenization temperatures range from 150° to 250°C for stage I fluids; 220° to 480°C for stage II fluids; 250° to 350°C for stage III fluids; 150° to 250°C for stage IV fluids and 90° to 250°C for stage V fluids. The coexistence of liquid-rich and vapour-rich inclusions in stages II and III minerals suggest that the hydrothermal fluids were boiling or effervescing. The coexistence of saturated and unsaturated inclusions in stages II and III minerals may be due to effervescence of a less saline fluid, whilst for stages IV and V it may be due to mixing of a highly saline fluid with a less saline fluid, or due to alternation of hydrostatic and lithostatic pressures at the time of trapping of the inclusions.  相似文献   

5.
《Applied Geochemistry》2002,17(6):735-750
Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite±fluorite±zeolites that is frequently capped by chalcedony±quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (⩽3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85 °C. Calcite deposition during the past several million years appears to have been at temperatures <30 °C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite δ18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from gradual cooling of nearby plutons. The physical restriction of the deposits (and, therefore, fluid flow) to fracture footwalls and cavity floors and the heterogeneous and limited distribution of the deposits provides compelling evidence that they do not reflect flooding of the thick UZ at Yucca Mountain. The textures and isotopic and chemical compositions of these mineral deposits are consistent with deposition in a UZ setting from meteoric waters percolating downward along fracture flow paths.  相似文献   

6.
Fracture minerals calcite, pyrite, gypsum, barite and quartz, formed during several events have been analysed for δ13C, δ18O, δ34S, 87Sr/86Sr, trace element chemistry and fluid inclusions in order to gain knowledge of the paleohydrogeological evolution of the Simpevarp area, south-eastern Sweden. This area is dominated by Proterozoic crystalline rocks and is currently being investigated by the Swedish Nuclear Fuel and Waste Management Co. (SKB) in order to find a suitable location for a deep-seated repository for spent nuclear fuel. Knowledge of the paleohydrogeological evolution is essential to understand the stability or evolution of the groundwater system over a time scale relevant to the performance assessment for a spent nuclear fuel repository. The ages of the minerals analysed range from the Proterozoic to possibly the Quaternary. The Proterozoic calcite and pyrite show inorganic and hydrothermal-magmatic stable isotope signatures and were probably formed during a long time period as indicated by the large span in temperatures (c. 200–360 °C) and salinities (0–24 wt.% eq. CaCl2), obtained from fluid inclusion analyses. The Paleozoic minerals were formed from organically influenced brine-type fluids at temperatures of 80–145 °C. The isotopic results indicate that low temperature calcite and pyrite may have formed during different events ranging in time possibly from the end of the Paleozoic until the Quaternary. Formation conditions ranging from fresh to brackish and saline waters have been distinguished based on calcite crystal morphologies. The combination of δ18O and crystal morphologies show that the fresh–saline water interface has changed considerably over time, and water similar to the present meteoric water and brackish seawater at the site, have most probably earlier been residing in the bedrock. Organic influence and closed system in situ microbial activity causing disequilibrium are indicated by extremely low δ13C (down to −99.7‰), extreme variation in δ34S (−42.5‰ to +60.8‰) and trace element compositions. The frequency of calcite low in δ13C and high in Mn, as well as pyrite with biogenically modified δ34S decreases with depth. Strontium isotopes have been useful to separate the different generations and the Sr isotope ratios in the groundwaters have been determined mainly by in situ water–rock interaction processes. The difficulty of separating late Paleozoic calcite from possibly recent calcite, and the fact that these calcites are usually found in the same fracture systems indicate that water conducting structures have been intermittently conductive from the Paleozoic and onwards. The methodology used has been successful in separating the different generations and characterising their formation conditions.  相似文献   

7.
The Ohtani and Kaneuchi deposits are tungsten-bearing quartz veins of hypothermal type which are hosted by Cretaceous granodiorite and sedimentary rocks respectively. Oxygen and carbon isotopic compositions were measured on minerals associated with the deposits to determine whether the ore-forming fluids were derived from related igneous bodies. The oxygen isotopic equilibrium temperatures of quartz-muscovite pairs within veins from the Ohtani and Kaneuchi deposits range from 530° to 190°C and from 400° to 300°C, respectively. The equilibrium temperatures of the granodiorite (600°C), greisen (590° to 530°C) and veins in the Ohtani deposit decrease in this order. The calculated oxygen isotopic composition of the Ohtani ore-forming fluid is around 12 (SMOW) above 500°C and lowers successively toward 3 as temperature decreases. The fluid at the earliest stage of mineralization could be in equilibrium with the granodiorite at about 600°C. These lines of evidence suggest that the granodiorite magma played a crucial role in the mineralization. The evolution trend of the Ohtani ore-forming fluid can be explained by a combined process of cooling due to heat conduction, adiabatic expansion and mixing of magmatic water with ground water. Calcites from the deposits have carbon isotopic ratios ranging from -11 to + 2 with the oxygen isotopic ratios in a narrow range. Since the CO2/CH4 fugacity ratio of the fluid is estimated to have been near unity, a slight fluctuation in fO2 caused the large variation in the carbon isotopic composition of calcite. The formation pressures for the Ohtani and Kaneuchi deposits are calculated to be 1.5 kb and 1.4 kb, respectively, on the basis of the difference between the pressure-dependent homogenization temperatures of fluid inclusions and the pressure-independent isotopic equilibrium temperatures. These values are reasonable for the depths in which hypothermal ore deposits have formed.  相似文献   

8.
This study reports a complex fluid and thermal history using petrography, electron microprobe, isotopic analysis and fluid inclusions in replacement minerals within gypsum pseudomorphs in Tithonian-Berriasian lacustrine deposits in Northern Spain. Limestones and dolostones, formed in the alkaline lakes, contain lenticularly shaped gypsum pseudomorphs, considered to form in an evaporative lake. The gypsum was replaced by quartz and non-ferroan calcite (Ca-2), which partially replaces the quartz. Quartz contains solid inclusions of a preexisting non-ferroan calcite (Ca-1), anhydrite and celestine. High homogenization temperatures (T h ) values and inconsistent thermometric behaviour within secondary fluid inclusion assemblages in quartz (147?C351°C) and calcite (108?C352°C) indicate high temperatures after precipitation and entrapment of lower temperature FIAs. Th are in the same range as other reequilibrated fluid inclusions from quartz veins in the same area that are related to Cretaceous hydrothermalism. Gypsum was replaced by anhydrite, likely during early burial. Later, anhydrite was partially replaced by Ca-1 associated with intermediate burial temperatures. Afterward, both anhydrite and Ca-1 were partially replaced by quartz and this by Ca-2. All were affected during higher temperature hydrothermalism and a CO2-H2O fluid. Progressive heating and hydrothermal pulses, involving a CO2-H2O fluid, produce the reequilibration of the FIAs, which was followed by uplift and cooling.  相似文献   

9.
Solid inclusions of halite and sylvite, formed during regional and contact metamorphism have been identified by microscopy and by electron microprobe analysis in rocks from Campolungo, Switzerland and Cornone di Blumone, Italy. The solid inclusions occur in several of the major minerals crystallized during metamorphism and have been observed as idiomorphic crystals and dendrites. The compositions measured in 100 analyses from Campolungo, Switzerland and 40 analyses from Cornone di Blumone, Italy extend across the two-phase region in the system, KCl-NaCl, indicating that the salt inclusions are high temperature precipitates. In both localities compositionally zoned and unzoned crystals have been found. Measured compositions on the temperature maximum of the two-phase region indicate at least 500° C which can be compared with 500°±20° C determined by Mercolli (1982) and Walther (1983) from the Mg content of calcites from Campolungo. The solid inclusions have been trapped apart from CO2-rich and saline, H2O-rich fluid inclusions which have been described by Mercolli (1982) as the earliest preserved fluid inclusions in the rocks. The early precipitation of salt minerals at Campolungo indicates that fluids were saturated with NaCl and KCl at 500° C and pressures of 2,000 bars or higher. Similar relationships exist between solid and fluid inclusions in the rocks of Cornone di Blumone which formed at temperatures as high as 800° C and pressures between 0.5 and 1 kilobar (Ulmer 1983). The entrapment of halite and sylvite as solid inclusions preserves the composition of the minerals which may therefore be useful as geothermometers.  相似文献   

10.
Graphite in deep crustal enderbitic (orthopyroxene + garnet + plagioclase + quartz) granulites (740°C, 8.9 kb) of Nilgiri hills, southern India were investigated for their spectroscopic and isotopic characteristics. Four types of graphite crystals were identified. The first type (GrI), which is interstitial to other mineral grains, can be grouped into two subtypes, GrIA and GrIB. GrIA is either irregular in shape or deformed, and rough textured with average δ13C values of −12.7 ± 0.4‰ (n = 3). A later generation of interstitial graphite (GrIB) shows polygonal crystal shapes and highly reflecting smooth surface features. These graphite grains are more common and have δ13C values of −11.9 ± 0.3‰ (n = 14). Both subtypes show well-defined Raman shifts suggesting a highly crystalline nature. Cores of interstitial graphite grains have, on average, lower δ13C values by ∼0.5‰ compared to that of the rim. The second type of graphite (GrII) occurs as solid inclusions in silicate minerals, commonly forming regular hexagonal crystals with a slightly disordered structure. The third type of graphite (GrIII) is associated with solid inclusions (up to 100 μm) that have decrepitation halos of numerous small (<15 μm) satellite fluid inclusions of pure CO2 with varying density (1.105 to 0.75 g/cm3). The fourth type of graphite (GrIV) is found as daughter crystals within primary type CO2-fluid inclusions in garnet and quartz. These fluid inclusions have a range of densities (1.05 to 0.90 g/cm3), but in general are significantly less dense than graphite-free primary, pure CO2 fluid inclusions (1.12 g/cm3). Raman spectral characteristics of graphite inside fluid inclusions suggest graphite crystallization at low temperature (∼ 500°C). The precipitation of graphite probably occurred during the isobaric cooling of CO2-rich peak metamorphic fluid as a result of oxyexsolution of oxide phases. The oxyexsolution process is evidenced by the magnetite-ilmenite granular exsolution textures and the systematic presence of numerous micron-sized rutile and other oxide inclusions in association with fluid inclusions within garnet, plagioclase, and quartz.The carbon isotope compositions of coexisting CO2 (in fluid inclusions) and graphite show a fractionation (α2CO−gr) of ∼6‰ in garnet, consistent with the existing theoretical estimates of α2CO−gr at 800°C. A subsequent generation of CO2 inclusions trapped in matrix quartz and quartz segregation have higher δ13C values, −4‰ and −2.9‰ respectively. Graphite in quartz segregations also has higher δ13C values (−9.8‰) than those in enderbite (−12.7‰). Micro-graphite crystals included in garnet, quartz (enderbite), and quartz (segregation) have average δ13C values of −11.1, −10.4, and −8.7‰ respectively, indicating progressive enrichment in 13C with a decrease in temperature of recrystallization of respective minerals. This progressive enrichment is also observed in carbon isotope compositions of fluid inclusion CO2, suggesting isotopic equilibrium during graphite precipitation from CO2 fluids. Thus, the carbon isotope record preserved in these rocks by the interstitial graphite, CO2 fluid in enderbite, graphite microcrystals, graphite in quartz segregation, and CO2 fluid in quartz segregation, suggests a temperature-controlled isotopic evolution. This evolution is in accordance with a closed system Rayleigh-type graphite precipitation process which progressively enriched residual CO2 in 13C.  相似文献   

11.
Processes controlling the composition of seafloor hydrothermal fluids in silicic back-arc or near-arc crustal settings remain poorly constrained despite growing evidence for extensive magmatic-hydrothermal activity in such environments. We conducted a survey of vent fluid compositions from two contrasting sites in the Manus back-arc basin, Papua New Guinea, to examine the influence of variations in host rock composition and magmatic inputs (both a function of arc proximity) on hydrothermal fluid chemistry. Fluid samples were collected from felsic-hosted hydrothermal vent fields located on Pual Ridge (PACMANUS and Northeast (NE) Pual) near the active New Britain Arc and a basalt-hosted vent field (Vienna Woods) located farther from the arc on the Manus Spreading Center. Vienna Woods fluids were characterized by relatively uniform endmember temperatures (273-285 °C) and major element compositions, low dissolved CO2 concentrations (4.4 mmol/kg) and high measured pH (4.2-4.9 at 25 °C). Temperatures and compositions were highly variable at PACMANUS/NE Pual and a large, newly discovered vent area (Fenway) was observed to be vigorously venting boiling (358 °C) fluid. All PACMANUS fluids are characterized by negative δDH2O values, in contrast to positive values at Vienna Woods, suggesting substantial magmatic water input to circulating fluids at Pual Ridge. Low measured pH (25 °C) values (∼2.6-2.7), high endmember CO2 (up to 274 mmol/kg) and negative δ34SH2S values (down to −2.7‰) in some vent fluids are also consistent with degassing of acid-volatile species from evolved magma. Dissolved CO2 at PACMANUS is more enriched in 13C (−4.1‰ to −2.3‰) than Vienna Woods (−5.2‰ to −5.7‰), suggesting a contribution of slab-derived carbon. The mobile elements (e.g. Li, K, Rb, Cs and B) are also greatly enriched in PACMANUS fluids reflecting increased abundances in the crust there relative to the Manus Spreading Center. Variations in alkali and dissolved gas abundances with Cl at PACMANUS and NE Pual suggest that phase separation has affected fluid chemistry despite the low temperatures of many vents. In further contrast to Vienna Woods, substantial modification of PACMANUS/NE Pual fluids has taken place as a result of seawater ingress into the upflow zone. Consistently high measured Mg concentrations as well as trends of increasingly non-conservative SO4 behavior, decreasing endmember Ca/Cl and Sr/Cl ratios with increased Mg indicate extensive subsurface anhydrite deposition is occurring as a result of subsurface seawater entrainment. Decreased pH and endmember Fe/Mn ratios in higher Mg fluids indicate that the associated mixing/cooling gives rise to sulfide deposition and secondary acidity production. Several low temperature (?80 °C) fluids at PACMANUS/NE Pual also show evidence for anhydrite dissolution and water-rock interaction (fixation of B) subsequent to seawater entrainment. Hence, the evolution of fluid compositions at Pual Ridge reflects the cumulative effects of water/rock interaction, admixing and reaction of fluids exsolved from silicic magma, phase separation/segregation and seawater ingress into upflow zones.  相似文献   

12.
Oxygen isotope microanalyses of authigenic quartz, in combination with temperatures of quartz precipitation constrained by fluid inclusion microthermometry and burial history modelling, are employed to trace the origin and evolution of pore waters in three distinct reservoirs of the Brae Formation in the Miller and Kingfisher Fields (North Sea). Oxygen isotope ratios of quartz cements were measured in situ in nine sandstone thin sections with a Cameca ims-4f ion microprobe. In conjunction with quartz cement paragenesis in the reservoirs, constrained from textural and cathodoluminescence (CL) microscopy studies, pore water evolution was reconstructed from the time of deposition of the sandstones in the Upper Jurassic until the present.CL photomicrographs of quartz overgrowths in the Brae Formation sandstones show three cement zones (A, B and C) which can be related to different oxygen isotope compositions: (1) the earliest, and thinnest, zone A (homogeneous CL pattern with probable δ18O values between +23‰ and +26‰—direct measurements were not possible) precipitated in the sandstones at temperatures <60 °C; (2) the second zone B (complex CL pattern and directly measured δ18O values between +15‰ and +18‰) precipitated in the sandstones most likely between 70 and 90 °C; (3) the third zone C (homogeneous CL pattern and directly measured δ18O values between +16‰ and +22‰) precipitated in the sandstones most likely at temperatures >90 °C. Calculated oxygen isotope compositions of pore waters show that zone A quartz cements, and enclosing concretionary calcite, precipitated from a meteoric-type fluid (∼−7‰) during shallow burial (<1.5 km). Zone B quartz cements precipitated from fluids which evolved in composition from a meteoric-type fluid (δ18O −7‰) to a more 18O-enriched fluid (δ18O −4‰) as burial continued to ∼3.0 km. Data from zone C quartz cements are consistent with further fluid evolution from δ18O −4‰ to basinal-type fluids with δ18O similar to the present-day formation water oxygen isotope composition (+0.6‰ at 4.0 km burial). A similar pore water evolution can be derived for all three reservoirs studied, indicating that hydrogeologic evolution was similar across sandstones of the whole Brae Formation.The quartz cement zones observed in the Brae Formation sandstones, and the pore water history derived for the area studied, is analogous to published petrographic and pore water evolution data from the nearby Brent Group reservoirs and from reservoirs located in the Haltenbanken area on the Atlantic margin offshore Norway. Considering quartz cement is a major porosity-occluding phase in many reservoir sandstones, and because pore waters both dissolve quartz and carry the dissolved silica to cementation sites, the data presented are valuable for improving the understanding and prediction of reservoir quality development in sandstones globally.  相似文献   

13.
The pilot hole of the Continental Deep Borehole (KTB) drilling project is located in the Bavarian Oberpfalz at the western margin of the Bohemian Massif. The 4-km deep borehole penetrated various paragneisses and minor orthogneisses with intercalations of amphibolites and metagabbros. The different lithologies have systematically different whole-rock oxygen isotope values and give little evidence for large scale water-rock interaction. Minor fluid interaction is well documented during retrograde metamorphism by non-equilibrium fractionations between refractory minerals (quartz, garnet and hornblende) and altered minerals (chlorite/biolite and feldspar). Ubiquitous vein mineralisation indicates fluid-induced retrogression at temperatures between 150°C and 400°C. The D values of hydroxylbearing minerals are very uniform in all lithologic units. The calculated hydrogen isotope composition of the fluid in equilibrium with matrix and vein minerals increases from -45 for metabasic rocks, to -20 for gneisses, to about -5 for vein minerals. The oxygen isotope composition of the fluid has been buffered by the rock and decreases with decreasing temperature because of increasing fractionations at low temperatures and low water-rock ratios. Modern fluids sampled from open cavities within the borehole have isotopic compositions that suggest a continuous fluid evolution during retrogression in a closed system. The 13C values of calcite and graphite also indicate closed system mixing processes.  相似文献   

14.
Detailed melt and fluid inclusion studies in quartz hosts from the Variscan Ehrenfriedersdorf complex revealed that ongoing fractional crystallization of the highly evolved H2O-, B-, and F-rich granite magma produced a pegmatite melt, which started to separate into two immiscible phases at about 720°C, 100 MPa. With cooling and further chemical evolution, the immiscibilty field expanded. Two conjugate melts, a peraluminous one and a peralkaline one, coexisted down to temperatures of about 490°C. Additionally, high-salinity brine exsolved throughout the pegmatitic stage, along with low-density vapor. Towards lower temperatures, a hydrothermal system gradually developed. Boiling processes occurred between 450 and 400°C, increasing the salinities of hydrothermal fluids at this stage. Below, the late hydrothermal stage is dominated by low-salinity fluids. Using a combination of synchrotron radiation-induced X-ray fluorescence analysis and Raman spectroscopy, the concentration of trace elements (Mn, Fe, Zn, As, Sb, Rb, Cs, Sr, Zr, Nb, Ta, Ag, Sn, Ta, W, rare earth elements (REE), and Cu) was determined in 52 melt and 8 fluid inclusions that are representative of distinct stages from 720°C down to 380°C. Homogenization temperatures and water contents of both melt and fluid inclusions are used to estimate trapping temperatures, thus revealing the evolutionary stage during the process. Trace elements are partitioned in different proportions between the two pegmatite melts, high-salinity brines and exsolving vapors. Concentrations are strongly shifted by co ncomitant crystallization and precipitation of ore-forming minerals. For example, pegmatite melts at the initial stage (700°C) have about 1,600 ppm of Sn. Concentrations in both melts decrease towards lower temperatures due to the crystallization of cassiterite between 650 and 550°C. Tin is preferentially fractionated into the peralkaline melt by a factor of 2–3. While the last pegmatite melts are low in Sn (64 ppm at 500°C), early hydrothermal fluids become again enriched with about 800 ppm of Sn at the boiling stage. A sudden drop in late hydrothermal fluids (23 ppm of Sn at 370°C) results from precipitation of another cassiterite generation between 400 and 370°C. Zinc concentrations in peraluminous melts are low (some tens of parts per million) and are not correlated with temperature. In coexisting peralkaline melts and high-T brines, they are higher by a factor of 2–3. Zinc continuously increases in hydrothermal fluids (3,000 ppm at 400°C), where the precipitation of sphalerite starts. The main removal of Zn from the fluid system occurs at lower temperatures. Similarly, melt and fluid inclusion concentrations of many other trace elements directly reflect the crystallization and precipitation history of minerals at distinctive temperatures or temperature windows.  相似文献   

15.
湖南东坡柴山-蛇形坪一带铅锌矿床流体包裹体研究   总被引：2，自引：1，他引：1  
东坡柴山-蛇形坪一带铅锌矿床位于千里山岩体西南侧的远接触带上,由脉状、柱状和席状的铅锌矿体组成,在矿体周围明显发生碳酸盐化和硅化作用。该带矿床中闪锌矿、萤石、石英和方解石内流体包裹体类型主要包括富液相包裹体、富气相包裹体和含子矿物包裹体;其流体包裹体的均一温度范围为140~395℃,在350℃、240~260℃和200~220℃处分别出现峰值,反映该期热液流体在形成脉状、柱状铅锌矿体过程中可能包含了不同的捕获事件,其中方解石内出现的气体包裹体同与其共生的液体包裹体的均一温度相近,两者均一温度范围主要集中在268~395℃,峰值为350℃,液相包裹体w(NaCleq)范围为9%~11%,表明流体发生过气液相分离的沸腾作用;闪锌矿、萤石、石英和方解石中流体包裹体w(NaCleq)范围为0~23%,峰值9%~10%。流体包裹体的均一温度和盐度特征与岩浆热液流体演化到裂隙阶段静水压力条件下的流体相近。闪锌矿中流体包裹体内存在方解石和白云石子矿物,表明铅锌矿的成矿作用发生在富集碳酸盐的热液流体中。千里山花岗岩体晚期释放的流体沿着不同的通道上升,当它冷却到低于400℃,这些地区产生了脆性裂隙,流体沿着裂隙继续上升,并且发生沸腾作用,因此,温度在340~400℃时,w(NaCleq)为7%左右的流体分成了w(NaCleq)约10%的液相流体和w(NaCleq)约0.02%的气相流体,由于温度和压力的迅速降低,成矿物质沿着裂隙和空洞沉淀成矿,形成了东坡矿区的脉状、柱状和席状的铅锌矿体。  相似文献   

16.
This paper discusses the largest electrum units precipitated in calcite of the final (“nonproductive”) stage of ore formation. Notably, during examination of the chemical composition of these gold grains, sphalerite and other minerals belonging to the early (“productive”) association have been found. The results of thermo- and cryometric investigations of fluid inclusions in calcite of the Agatovskoe deposit have indicated that in the composition of two-phase fluid solutions of admixtures, NaCl, KCl, and MgCl dominated. This is evidenced by chloride eutectics of the admixture solutions in the temperature interval from −35 to −39°C. The complete homogenization of the fluid admixtures takes place in a narrow temperature interval (from 206 to 213°C) and concentration of salts is 3.7–6.0 mass % in NaCl equivalent. The density of the fluid changes starting from 0.88–0.89 g/cm3. The derived homogenization temperatures correspond to the temperatures of gold deposition, since the pressure during formation of gold veins in the deposit was small.  相似文献   

17.
Ordovician limestones in the Francon quarr on the island of Montreal, Quebec, are host to three sills of Cretaceous age composed of phonolite that has been extensively altered to dawsonite. An interesting feature of the sills is the presence of abundant vugs containing a wide variety of minerals, including several in which one or more high field strength elements (Zr, Hf, Nb, Ti) is a major component. The most important of these latter minerals is weloganite, a rare strontium zirconium hydrous carbonate, first identified in the Francon, quarry. Four types of inclusions have been recognized in vug minerals: aqueous, aqueous-carbonic, carbonic and solidbearing. Aqueous inclusions homogenize at temperatures mainly between 70° and 170°C and between 230° and 390°C. The homogenization temperatures of primary inclusions cluster around 350°C. Aqueous inclusions and the aqueous phase in aqueous-carbonic inclusions have salinities ranging between 10 and 24 eq.wt.% NaCl equivalent. Primary aqueous-carbonic inclusions have low XCO2 (<0.03), whereas secondary aqueous-carbonic inclusions can have high XCO2 (>0.7); carbonic inclusions are all secondary. Nahcolite, dawsonite and weloganite occur as daughter minerals or trapped solids. Nahcolite and possibly natron or mirabilite appear to form in frozen inclusions. Analyses of fluid inclusion decrepitates detected high concentrations of Na, Cl, Al, S, and C. The extraordinarily high concentration of Al in the fluid (possibly exceeding 1 wt.%) suggests a pH of approximately 10. Pressure and temperature conditions, estimated from stratigraphic reconstruction and the isochores of primary aqueous fluid inclusions, were 450 bar and 360 to 400°C, respectively. The relatively high temperatures and compositions of primary fluid inclusions suggest that vug filling was the result of mineral precipitation from an orthomagmatic fluid. A model is proposed in which a partially crystallized phonolite melt started exsolving a homogeneous low XCO2 fluid immediately prior to or after intrusion. Sodium, aluminium, chlorine, fluorine, sulphur and HFSE elements such as Zr, Hf, Nb and Ti were partitioned into the hydrous phase, in the case of Zr, possibly to a concentration of 300 ppm. The near horizontal orientation of the sills and the chilled margins, produced by quenching of the magma, created a tight seal that inhibited escape of the fluids. As a result, the phonolite stewed in its own juices long after crystallization, giving rise to widespread replacement of primary igneous minerals by dawsonite, and precipitation of this and other minerals in vugs. Once the sills had colled to temperatures between 200 and 300°C, the aqueous fluid exsolved a high CO2 fluid which was trapped as the secondary three-phase type II and type III inclusions. Decreasing temperature is considered to have been the principal control of mineralization, although in the case of the lower temperature minerals, decreased bicarbonate or carbonate ion activity, and a lower dielectric constant, as a result of CO2 exsolution, may have played a role in the deposition of HFSE-bearing minerals.  相似文献   

18.
Many of the zinc-lead deposits of NE Washington State are poorly known examples of Mississippi Valley Type (MVT) mineralization. This study compares inclusion fluids from the Josephine Breccia ores with the later cross-cutting sulfide-bearing quartz veins. The breccia ores are cemented mainly by open space fillings of dolomite, sphalerite, quartz, galena, jasperoid and calcite. Replacement is of minor importance. Ore and gangue deposition occurred over the range 150–250 °C with most of the temperatures less than 200 °C. The aqueous brines typically contain 17–23 equivalent weight percent NaCl with often substantial amounts of Ca and/or Mg chlorides. Homogenization temperatures do not delineate any cooling or paragenetic sequence. The cross-cutting vein quartz contains CO2-rich inclusions with overall densities usually less than 0.7 g/cc and homogenization temperatures from 250–325 °C. Sulfur isotope analyses yield two populations with the quartz vein ores being lighter (<13 permil CDT) than the average for the conformable ores. The later veins are not remobilized MVT sulfides but represent a separate, high-silver period of mineralization.  相似文献   

19.
Although commonly utilized in continental geothermal work, the water-hydrogen and methane-hydrogen isotope geothermometers have been neglected in hydrothermal studies. Here we report δD-CH4 and δD-H2 values from high-temperature, black smoker-type hydrothermal vents and low-temperature carbonate-hosted samples from the recently discovered Lost City Hydrothermal Field. Methane deuterium content is uniform across the dataset at − 120 ± 12‰. Hydrogen δD values vary from − 420‰ to − 330‰ at high-temperature vents to − 700‰ to − 600‰ at Lost City. The application of several geothermometer equations to a suite of hydrothermal vent volatile samples reveals that predicted temperatures are similar to measured vent temperatures at high-temperature vents, and 20-60 °C higher than those measured at the Lost City vents. We conclude that the overestimation of temperature at Lost City reflects 1) that methane and hydrogen are produced by serpentinization at > 110 °C, and 2) that isotopic equilibrium at temperatures < 70 °C is mediated by microbial sulfate reduction. The successful application of hydrogen isotope geothermometers to low-temperature Lost City hydrothermal samples encourages its employment with low-temperature diffuse hydrothermal fluids.  相似文献   

20.
Oxygen isotope exchange between minerals during metamorphism can occur in either the presence or the absence of aqueous fluids. Oxygen isotope partitioning among minerals and fluid is governed by both chemical and isotopic equilibria during these processes, which progress by intragranular and intergranular diffusion as well as by surface reactions. We have carried out isotope exchange experiments in two- and three-phase systems, respectively, between calcite and tremolite at high temperatures and pressures. The two-phase system experiments were conducted without fluid either at 1 GPa and 680 °C for 7 days or at 500 MPa and 560 °C for 20 days. Extrapolated equilibrium fractionations between calcite and tremolite are significantly lower than existing empirical estimates and experimental determinations in the presence of small amounts of fluid, but closely match calculated fractionations by means of the increment method for framework oxygen in tremolite. The small fractionations measured in the direct calcite–tremolite exchange experiments are interpreted by different rates of oxygen isotope exchange between hydroxyl oxygen, framework oxygen and calcite during the solid–solid reactions where significant recrystallization occurs. The three-phase system experiments were accomplished in the presence of a large amount of fluid (CO2+H2O) at 500 MPa and 560 °C under conditions of phase equilibrium for 5, 10, 20, 40, 80, 120, 160, and 200 days. The results show that oxygen isotope exchange between minerals and fluid proceeds in two stages: first, through a mechanism of dissolution-recrystallization and very rapidly; second, through a mechanism of diffusion and very slowly. Synthetic calcite shows a greater rate of isotopic exchange with fluid than natural calcite in the first stage. The rate of oxygen diffusion in calcite is approximately equal to or slightly greater than that in tremolite in the second stage. A calculation using available diffusion coefficients for calcite suggests that grain boundary diffusion, rather than volume diffusion, has been the dominant mechanism of oxygen transport between the fluid and the mineral grains in the later stage.Editorial responsibility: T.L. Grove  相似文献   

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