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1.
Pyrite and marcasite were precipitated by both slow addition of aqueous Fe 2+ and SiO 32− to an H 2S solution and by mixing aqueous Fe 2+ and Na 2S 4 solutions at 75°C. H 2S 2 or HS 2− and H 2S 4 or HS 4− were formed in the S 2O 32− and Na 2S 4 experiments, respectively. Marcasite formed at pH < pK 1 of the polysulfide species present (for H2S2, pK1 = 5.0; for H2S4, pK1 = 3.8 at 25° C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H 2S 2 and HS 2 are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures. The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H2S2 and HS2 are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS2 and S22− are strongly attracted to the positive pyrite growth sites. Masking of 1πg* electrons in the S2 group by the protons makes HS2 and H2S2 isoelectronic with AsS2− and As22−, respectively (
et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated. Marcasite occurs abundantly only for conditions below pH 5 and where H2S2 was formed near the site of deposition by either partial oxidation of aqueous H2S by O2 or by the reaction of higher oxidation state sulfur species that are reactive with H2S at the conditions of formation e.g., S2O32− but not SO42−. The temperature of formation of natural marcasite may be as high as 240°C (
and
, 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C (
, 1973;
and
, 1985). 相似文献
2.
A combined fluid inclusion and mineral thermobarometric study in groups of synchronous inclusions in quartz within weakly foliated granites from the Chottanagpur Gneissic Complex, India, reveals super dense carbonic (CO 2 with minor CH 4 and H 2O) inclusions and hypersaline (H 2O–NaCl ± NaHCO 3) inclusions, with halite- and nahcolite daughter phases. This study documents the highest density (1.115 g cm − 3) CO 2 fluids ever reported in granites. Fluid isochores, constructed from CO 2 (± CH 4) and halite-bearing inclusions, coupled with two-feldspar thermometry constrain the minimum P–T at 8 kbar/ 750 °C for fluid entrapment in granites. By contrast, the carbonic inclusions in quartz from granite-hosted metapelite enclaves contain substantial CH 4 (up to 30 mol%), and the entrapment pressure ( 4.3 kbar/600 °C) is considerably lower compared to those in the granites. By implication, the sillimanite-free granites were not derived from the metapelitic enclaves, and instead were formed by partial melting of fluid-heterogeneous lower crustal protoliths, with fluid entrapment at magmatic conditions. 相似文献
3.
The abiotic synthesis of organic compounds in seafloor hydrothermal systems is one mechanism through which the subsurface environment could be supplied with reduced carbon. A flow-through, fixed-bed laboratory reactor vessel, the Catalytic Reactor Vessel (CRV) system, has been developed to investigate mineral–surface promoted organic synthesis at temperatures up to 400°C and pressures up to 30 MPa, conditions relevant to seafloor hydrothermal systems. Here we present evidence that metastable methanol can be directly synthesized from a gas-rich CO 2–H 2–H 2O mixture in the presence of a mineral substrate. Experiments have been performed without a substrate, with quartz, and with a mixture of quartz and magnetite. Temperatures and pressures in the experiments ranged from 200°C to 350°C and from 15 to 18 MPa, respectively. Maximum conversion of 5.8×10 −4% CO 2 to CH 3OH per hour was measured using a mixture of magnetite and quartz in the reactor. After passivation of the stainless steel reactor vessel, experiments demonstrate that methanol is formed at temperatures up to 350°C in the presence of magnetite, and that the formation rate decreases over time. The experiments also show a loss of surface reactivity at 310°C and a regeneration of surface reactivity with increased temperature up to 350°C. Concentrations of CO 2 and H 2 used in the experiments simulate periodic, localized and dynamic conditions occurring within the seafloor during and immediately following magmatic diking events. High concentrations of CO 2 and H 2 may be generated by dike injection accompanied by exsolution of CO 2 and reaction of dissolved H 2O with FeO in the magma to form H 2. The experiments described here examine how the ephemeral formation of an H 2–CO 2-rich vapor phase within seafloor hydrothermal systems may supply reactants for abiotic organic synthesis reactions. These experiments show that the presence of specific minerals can promote the abiotic synthesis of simple organic molecules from common inorganic reactants such H 2O, CO 2 and H 2 under geologically realistic conditions. 相似文献
4.
A detailed fluid inclusion study has been carried out on the hydrocarbon-bearing fluids found in the peralkaline complex, Lovozero. Petrographic, microthermometric, laser Raman and bulk gas data are presented and discussed in context with previously published data from Lovozero and similar hydrocarbon-bearing alkaline complexes in order to further understand the processes which have generated these hydrocarbons. CH 4-dominated inclusions have been identified in all Lovozero samples. They occur predominantly as secondary inclusions trapped along cleavage planes and healed fractures together with rare H 2O-dominant inclusions. They are consistently observed in close association with either arfvedsonite crystals, partially replaced by aegirine, aegirine crystals or areas of zeolitization. The majority of inclusions consist of a low-density fluid with CH 4 homogenisation temperatures between −25 and −120 °C. Those in near-surface hand specimens contain CH 4+H 2 (up to 40 mol%)±higher hydrocarbons. However, inclusions in borehole samples contain CH 4+higher hydrocarbons±H 2 indicating that, at depth, higher hydrocarbons are more likely to form. Estimated entrapment temperatures and pressures for these inclusions are 350 °C and 0.2–0.7 kbar. A population of high-density, liquid, CH 4-dominant inclusions have also been recorded, mainly in the borehole samples, homogenising between −78 and −99 °C. These consist of pure CH 4, trapped between 1.2 and 2.1 kbar and may represent an early CH 4-bearing fluid overprinted by the low-density population. The microthermometric and laser Raman data are in agreement with bulk gas data, which have recorded significant concentrations of H 2 and higher hydrocarbons up to C 6H 12 in these samples. These data, combined with published isotopic data for the gases CH 4, C 2H 6, H 2, He and Ar indicate that these hydrocarbons have an abiogenic, crustal origin and were generated during postmagmatic, low temperature, alteration reactions of the mineral assemblage. This would suggest that these data favour a model for formation of hydrocarbons through Fischer–Tropsch type reactions involving an early CO 2-rich fluid and H 2 derived from alteration reactions. This is in contrast to the late-magmatic model suggested for the formation of hydrocarbons in the similar peralkaline intrusion, Ilímaussaq, at temperatures between 400 and 500 °C. 相似文献
5.
In this paper the first fluid-inclusion data are presented from Late Archaean Scourian granulites of the Lewisian complex of mainland northwest Scotland. Pure CO 2 or CO 2-dominated fluid inclusions are moderately abundant in pristine granulites. These inclusions show homogenization temperatures ranging from − 54 to + 10 °C with a very prominent histogram peak at − 16 to − 32 °C. Isochores corresponding to this main histogram peak agree with P-T estimates for granulite-facies recrystallization during the Badcallian (750–800 °C, 7–8 kbar) as well as with Inverian P-T conditions (550–600 °C, 5 kbar). The maximum densities encountered could correspond to fluids trapped during an early, higher P-T phase of the Badcallian metamorphism (900–1000 °C, 11–12 kbar). Homogenization temperatures substantially higher than the main histogram peak may represent Laxfordian reworking (≤ 500 °C, < 4 kbar). In the pristine granulites, aqueous fluid inclusions are of very subordinate importance and occur only along late secondary healed fractures. In rocks which have been retrograded to amphibolite facies from Inverian and/or Laxfordian shear zones, CO 2 inclusions are conspicuously absent; only secondary aqueous inclusions are present, presumably related to post-granulite hydration processes. These data illustrate the importance of CO 2-rich fluids for the petrogenesis of Late Archaean granulites, and demonstrate that early fluid inclusions may survive subsequent metamorphic processes as long as no new fluid is introduced into the system. 相似文献
6.
In order to identify and characterise fluids associated with metamorphic rocks from the Chaves region (North Portugal), fluid inclusions were studied in quartz veinlets, concordant with the main foliation, in graphitic-rich and nongraphitic-rich lithologies from areas with distinct metamorphic grade. The study indicates multiple fluid circulation events with a variety of compositions, broadly within the C–H–O–N–salt system. Primary fluid inclusions in quartz contain low salinity aqueous–carbonic, H 2O–CH 4–N 2–NaCl fluids that were trapped near the peak of regional metamorphism, which occurred during or immediately after D2. The calculated P– T conditions for the western area of Chaves (CW) is P=300–350 MPa and T500 °C, and for the eastern area (CE), P=200–250 MPa and T=400–450 °C. A first generation of secondary fluid inclusions is restricted to discrete cracks at the grain boundaries of quartz and consists of low salinity aqueous–carbonic, H 2O–CO 2–CH 4–N 2–NaCl fluids. P– T conditions from the fluid inclusions indicate that they were trapped during a thermal event, probably related with the emplacement of the two-mica granites. A second generation of secondary inclusions occurs in intergranular fractures and is characterised by two types of aqueous inclusions. One type is a low salinity, H2O–NaCl fluid and the second consists of a high salinity, H2O–NaCl–CaCl2 fluid. These fluid inclusions are not related to the metamorphic process and have been trapped after D3 at relatively low P (hydrostatic)–T conditions (P<100 MPa and T<300 °C). Both the early H2O–CH4–N2–NaCl fluids in quartz from the graphitic-rich lithologies and the later H2O–CO2–CH4–N2–NaCl carbonic fluid in quartz from graphitic-rich and nongraphitic-rich lithologies seem to have a common origin and evolution. They have low salinity, probably resulting from connate waters that were diluted by the water released from mineral dehydration during metamorphism. Their main component is water, but the early H2O–CH4–N2–NaCl fluids are enriched in CH4 due to interaction with the C-rich host rocks. From the early H2O–CH4–N2–NaCl to the later aqueous–carbonic H2O–CO2–CH4–N2–NaCl fluids, there is an enrichment in CO2 that is more significant for the fluids associated with nongraphitic-rich lithologies. The aqueous–carbonic fluids, enriched in H2O and CH4, are primarily associated with graphitic-rich lithologies. However, the aqueous–carbonic CO2-rich fluids were found in both graphitic and nongraphitic-rich units from both the CW and CE studied areas, which are of medium and low metamorphic grade, respectively. 相似文献
7.
Three types of fluid inclusions have been identified in olivine porphyroclasts in the spinel harzburgite and lherzolite xenoliths from Tenerife: pure CO 2 (Type A); carbonate-rich CO 2–SO 2 mixtures (Type B); and polyphase inclusions dominated by silicate glass±fluid±sp±silicate±sulfide±carbonate (Type C). Type A inclusions commonly exhibit a “coating” (a few microns thick) consisting of an aggregate of a platy, hydrous Mg–Fe–Si phase, most likely talc, together with very small amounts of halite, dolomite and other phases. Larger crystals (e.g. (Na,K)Cl, dolomite, spinel, sulfide and phlogopite) may be found on either side of the “coating”, towards the wall of the host mineral or towards the inclusion center. These different fluids were formed through the immiscible separations and fluid–wall-rock reactions from a common, volatile-rich, siliceous, alkaline carbonatite melt infiltrating the upper mantle beneath the Tenerife. First, the original siliceous carbonatite melt is separated from a mixed CO 2–H 2O–NaCl fluid and a silicate/silicocarbonatite melt (preserved in Type A inclusions). The reaction of the carbonaceous silicate melt with the wall-rock minerals gave rise to large poikilitic orthopyroxene and clinopyroxene grains, and smaller neoblasts. During the metasomatic processes, the consumption of the silicate part of the melt produced carbonate-enriched Type B CO 2–SO 2 fluids which were trapped in exsolved orthopyroxene porphyroclasts. At the later stages, the interstitial silicate/silicocarbonatite fluids were trapped as Type C inclusions. At a temperature above 650 °C, the mixed CO 2–H 2O–NaCl fluid inside the Type A inclusions were separated into CO 2-rich fluid and H 2O–NaCl brine. At T<650 °C, the residual silicate melt reacted with the host olivine, forming a reaction rim or “coating” along the inclusion walls consisting of talc (or possibly serpentine) together with minute crystals of NaCl, KCl, carbonates and sulfides, leaving a residual CO 2 fluid. The homogenization temperatures of +2 to +25 °C obtained from the Type A CO 2 inclusions reflect the densities of the residual CO 2 after its reactions with the olivine host, and are unrelated to the initial fluid density or the external pressure at the time of trapping. The latter are restricted by the estimated crystallization temperatures of 1000–1200 °C, and the spinel lherzolite phase assemblage of the xenolith, which is 0.7–1.7 GPa. 相似文献
8.
Minor granulites (believed to be pre-Triassic), surrounded by abundant amphibolite-facies orthogneiss, occur in the same region as the well-documented Triassic high- and ultrahigh-pressure (HP and UHP) eclogites in the Dabie–Sulu terranes, eastern China. Moreover, some eclogites and garnet clinopyroxenites have been metamorphosed at granulite- to amphibolite-facies conditions during exhumation. Granulitized HP eclogites/garnet clinopyroxenites at Huangweihe and Baizhangyan record estimated eclogite-facies metamorphic conditions of 775–805 °C and ≥15 kbar, followed by granulite- to amphibolite-facies overprint of ca. 750–800 °C and 6–11 kbar. The presence of (Na, Ca, Ba, Sr)-feldspars in garnet and omphacite corresponds to amphibolite-facies conditions. Metamorphic mineral assemblages and P– T estimates for felsic granulite at Huangtuling and mafic granulite at Huilanshan indicate peak conditions of 850 °C and 12 kbar for the granulite-facies metamorphism and 700 °C and 6 kbar for amphibolite-facies retrograde metamorphism. Cordierite–orthopyroxene and ferropargasite–plagioclase coronas and symplectites around garnet record a strong, rapid decompression, possibly contemporaneous with the uplift of neighbouring HP/UHP eclogites. Carbonic fluid (CO2-rich) inclusions are predominant in both HP granulites and granulitized HP/UHP eclogites/garnet clinopyroxenites. They have low densities, having been reset during decompression. Minor amounts of CH4 and/or N2 as well as carbonate are present. In the granulitized HP/UHP eclogites/garnet clinopyroxenites, early fluids are high-salinity brines with minor N2, whereas low-salinity fluids formed during retrogression. Syn-granulite-facies carbonic fluid inclusions occur either in quartz rods in clinopyroxene (granulitized HP garnet clinopyxeronite) or in quartz blebs in garnet and quartz matrices (UHP eclogite). For HP granulites, a limited number of primary CO2 and mixed H2O–CO2(liquid) inclusions have also been observed in undeformed quartz inclusions within garnet, orthopyroxene, and plagioclase which contain abundant, low-density CO2±carbonate inclusions. It is suggested that the primary fluid in the HP granulites was high-density CO2, mixed with a significant quantity of water. The water was consumed by retrograde metamorphic mineral reactions and may also have been responsible for metasomatic reactions (“giant myrmekites”) occurring at quartz–feldspar boundaries. Compared with the UHP eclogites in this region, the granulites were exhumed in the presence of massive, externally derived carbonic fluids and subsequently limited low-salinity aqueous fluids, probably derived from the surrounding gneisses. 相似文献
9.
Coexisting melt (MI), fluid-melt (FMI) and fluid (FI) inclusions in quartz from the Oktaybrskaya pegmatite, central Transbaikalia, have been studied and the thermodynamic modeling of PVTX-properties of aqueous orthoboric-acid fluids has been carried out to define the conditions of pocket formation. At room temperature, FMI in early pocket quartz and in quartz from the coarse-grained quartz–oligoclase host pegmatite contain crystalline aggregates and an orthoboric-acid fluid. The portion of FMI in inclusion assemblages decreases and the volume of fluid in inclusions increases from the early to the late growth zones in the pocket quartz. No FMI have been found in the late growth zones. Significant variations of solid/fluid ratios in the neighboring FMI result from heterogeneous entrapment of coexisting melts and fluids by a host mineral. Raman spectroscopy, SEM EDS and EMPA indicate that the crystalline aggregates in FMI are dominated by mica minerals of the boron-rich muscovite–nanpingite CsAl 2[AlSi 3O 10](OH,F) 2 series as well as lepidolite. Topaz, quartz, potassium feldspar and several unidentified minerals occur in much lower amounts. Fluid isolations in FMI and FI have similar total salinity (4–8 wt.% NaCl eq.) and H 3BO 3 contents (12–16 wt.%). The melt inclusions in host-pegmatite quartz homogenize at 570–600 °C. The silicate crystalline aggregates in large inclusions in pocket quartz completely melt at 615 °C. However, even after those inclusions were significantly overheated at 650±10 °C and 2.5 kbar during 24 h they remained non-homogeneous and displayed two types: (i) glass+unmelted crystals and (ii) fluid+glass. The FMI glasses contain 1.94–2.73 wt.% F, 2.51 wt.% B 2O 3, 3.64–5.20 wt.% Cs 2O, 0.54 wt.% Li 2O, 0.57 wt.% Ta 2O 5, 0.10 wt.% Nb 2O 5, 0.12 wt.% BeO. The H 2O content of the glass could exceed 12 wt.%. Such compositions suggest that the residual melts of the latest magmatic stage were strongly enriched in H 2O, B, F, Cs and contained elevated concentrations of Li, Be, Ta, and Nb. FMI microthermometry showed that those melts could have crystallized at 615–550 °C. Crystallization of quartz–feldspar pegmatite matrix leads to the formation of H2O-, B- and F-enriched residual melts and associated fluids (prototypes of pockets). Fluids of different compositions and residual melts of different liquidus–solidus P–T-conditions would form pockets with various internal fluid pressures. During crystallization, those melts release more aqueous fluids resulting in a further increase of the fluid pressure in pockets. A significant overpressure and a possible pressure gradient between the neighboring pockets would induce fracturing of pockets and “fluid explosions”. The fracturing commonly results in the crushing of pocket walls, formation of new fractures connecting adjacent pockets, heterogenization and mixing of pocket fluids. Such newly formed fluids would interact with a primary pegmatite matrix along the fractures and cause autometasomatic alteration, recrystallization, leaching and formation of “primary–secondary” pockets. 相似文献
10.
The stability and phase relations of phengitic muscovite in a metapelitic bulk composition containing a mixed H 2O+CO 2 fluid were investigated at 6.5–11 GPa, 750–1050°C in synthesis experiments performed in a multianvil apparatus. Starting material consisted of a natural calcareous metapelite from the coesite zone of the Dabie Mountains, China, ultrahigh-pressure metamorphic complex that had experienced peak metamorphic pressures greater than 3 GPa. The sample contains a total of 2.1 wt.% H 2O and 6.3 wt.% CO 2 bound in hydrous and carbonate minerals. No additional fluid was added to the starting material. Phengite is stable in this bulk composition from 6.5 to 9 GPa at 900°C and coexists with an eclogitic phase assemblage consisting of garnet, omphacite, coesite, rutile, and fluid. Phengite dehydrates to produce K-hollandite between 8 and 11 GPa, 750–900°C. Phengite melting/dissolution occurs between 900°C and 975°C at 6.5–8 GPa and is associated with the appearance of kyanite in the phase assemblage. The formation of K-hollandite is accompanied by the appearance of magnesite and topaz-OH in the phase assemblage as well as by significant increases in the grossular content of garnet (average Xgrs=0.52, Xpy=0.19) and the jadeite content of omphacite ( Xjd=0.92). Mass balance indicates that the volatile content of the fluid phase changes markedly at the phengite/K-hollandite phase boundary. At P≤8 GPa, fluid coexisting with phengite appears to be relatively CO 2-rich (XCO 2/XH 2O=2.2), whereas fluid coexisting with K-hollandite and magnesite at 11 GPa is rich in H 2O (XCO 2/XH 2O=0.2). Analysis of quench material and mass balance calculations indicate that fluids at all pressures and temperatures examined contain an abundance of dissolved solutes (approximately 40 mol% at 8 GPa, 60 mol% at 11 GPa) that act to dilute the volatile content of the fluid phase. The average phengite content of muscovite is positively correlated with pressure and ranges from 3.62 Si per formula unit (pfu) at 6.5 GPa to 3.80 Si pfu at 9 GPa. The extent of the phengite substitution in muscovite in this bulk composition appears to be limited to a maximum of 3.80–3.85 Si pfu at P=9 GPa. These experiments show that phengite should be stable in metasediments in mature subduction zones to depths of up to 300 km even under conditions in which aH 2O1. Other high-pressure hydrous phases such as lawsonite, MgMgAl-pumpellyite, and topaz-OH that may form in subducted sediments do not occur within the phengite stability field in this system, and may require more H 2O-rich fluid compositions in order to form. The wide range of conditions under which phengite occurs and its participation in mixed volatile reactions that may buffer the composition of the fluid phase suggest that phengite may significantly influence the nature of metasomatic fluids released from deeply subducted sediments at depths of up to 300 km at convergent plate boundaries. 相似文献
11.
The stability fields of analcime and analcime+quartz have been investigated using conventional hydrothermal techniques, over the approximate range of conditions 160–600 °C and 500–5000 bars fluid pressure. The dehydration of analcime (Na 2Al 2Si 3·3O 11·6 · nH 2O) to albite, nepheline and H 2O occurs at temperatures of 492±5 °C at 500 bars, 538±5 °C at 1000 bars, 578±5 °C at 2000 bars and 598±5 °C at 3000 bars. In the presence of quartz, analcine dehydrates to highly disordered albite and H 2O at about 200 °C and 2000 bars, 196°±5 °C and 3000 bars, about 190 °C and 4000 bars, and 183±5 °C at 5000 bars Pfluid. The synthetic phase equilibria appear to be compatible with field observations that primary analcimes occur as phenocrysts or in groundmass in some volcanic and hypabyssal rocks and secondary analcimes in sedimentary, hydrothermally altered and low-grade metamorphic rocks. 相似文献
12.
Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na +), 0.032 (K +), 0.165 (Li +), 0.292 (Ca 2+, Mg 2+), −0.139 (SO 42−), and −0.009 (NO 3−). A set of polynomial equations has been derived which can be used to calculate λ SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ SiO2(aq)−i) and the surface electrostatic field ( Zi/ re,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ SiO2(aq) in the Na---K---Ca---Mg---Cl---SO 4---HCO 3---SiO 2---H 2O system, over a large range of salt concentrations and up to temperatures of 250°C. 相似文献
13.
The results of the 7 years (1994–2000) of monthly monitoring of spring water before and during eruptions show response to volcanic activity. Low salinity and temperature characterize most of the springs, which are located on the flanks of Popocatepetl Volcano. The pH ranges from 5.8 to 7.8 and temperature from 3 to 36 °C. Oxygen and hydrogen isotopic data show that the water is of meteoric origin, but SO 42−, Cl −, F −, HCO 3−, B, and SO 42−/Cl − variations precede main eruptive activity, which is considered linked to influx of magmatic gases and acid fluids that react with sublimates and host rock and mix with the large water system. Na +, Ca 2+, SiO 2 and Mg 2+ concentrations in the water also increased before eruptive activity. The computed partial pressure of CO 2 in equilibrium with spring waters shows values higher than air-saturated water (ASW), with the highest values up to 0.73 bar of pCO 2. Boron is detected in the water only preceding the larger eruptions. When present, boron concentration is normally under health standard limits, but in two cases the concentration was slightly above. Other components are within health standard limits, except for F − in one spring. 相似文献
14.
Recovery of highly viscous oil from some of the deeper oil sand deposits of northern Alberta, Canada, is made possible through injection of heat by steam or hot water flooding of the reservoirs. The rise in temperature lowers the viscosity of the bitumen allowing it to be produced. The increase in temperature accelerates the reactions between the matrix and pore minerals of the formation and can produce reaction products which can significantly alter the permeability of the reservoir. If carbonate minerals are present in the reservoir, inorganic CO 2 may also be a reaction product. The Grand Rapids reservoir consists of relatively clean quartz sand containing 7 wt.% kaolinite, 1 wt.% calcite and a trace of smectite. Core floods of this sand by a neutral NaCl brine at 265°C, 8.2-MPa overburden pressure, 6.0-MPa fluid pressure and a flow velocity of 0.4 pore volumes per hour were used to determine the potential for hydrothermal reactions between clays and carbonate minerals in a natural reservoir sand. Reaction progress was followed by continuous sampling of the production fluids. The produced water was analyzed and the phase chemistry was calculated back to the run conditions using the computer code SOLMNEQF. Mass-balance considerations on produced total inorganic carbon (TIC) show that calcite broke down very quickly, the maximum in CO2 production occurring after only one pore volume of fluid had passed through the core. The Ca released from the breakdown of calcite was incorporated in the formation of smectite as was shown by post-run clay mineral analysis by the following unbalanced chemical reaction: calcite+kaolinite+H4Si04Ca-smectite+H20+CO2 Silica was supplied by the dissolution of quartz. Silica concentrations analyzed in the production fluid were depressed from those predicted by previously published quartz rate equations because of the rapid rate of smectite synthesis. These observations were used to formulate the following model for the passage of the first pore volume of NaCl brine through the core. Initially calcite is present throughout the core. As the brine enters the inlet of the core, it equilibrates with calcite. The brine remains in equilibrium with calcite throughout the core as quartz and kaolinite react to form smectite. This model was tested with the computer code PATH.UBC using CO2 production as a measure of the progress variable ξ. A best fit was achieved to the produced fluid chemistry by varying relative dissolution rates of kaolinite and quatz and varying the suppression of precipitation of certain minerals. 相似文献
15.
As is typical of ultra-high pressure (UHP) terrains, the regional extent of the UHP terrain in the Dabieshan of central China is highly speculative, since the volume of eclogites and paragneisses preserving unequivocal evidence of coesite and/or diamond stability is very small. By contrast, the common garnet ( XMn=0.18–0.45)–phengite (Si=3.2–3.35)–zoned epidote (Ps 38–97)–biotite–titanite–two feldspars–quartz assemblages in the more extensive orthogneisses have been previously thought to have formed under low P– T conditions of ca. 400±50°C at 4 kbar. However, certain orthogneiss samples preserve garnets with XCa up to 0.50, rutile inclusions within titanite or epidote and relict phengite inclusions within epidote with Si contents p.f.u. of up to 3.49 — overlapping with the highest values (3.49–3.62) recorded for phengites in samples of undoubted UHP schists. These and other mineral composition features (such as A-site deficiencies in the highest Si phengites, Na in garnets linked to Y+Yb substitution and Al F Ti −1 O −1 substitution in titanites) are taken to be pointers towards the orthogneisses having experienced a similar metamorphic evolution to the associated UHP schists and eclogites. Re-evaluated garnet–phengite and garnet–biotite Fe/Mg exchange thermometry and calculated 5 rutile+3 grossular+2SiO 2+H 2O=5 titanite+2 zoisite equilibria indicate that the orthogneisses may indeed have followed a common subduction-related clockwise P– T path with the UHP paragneisses and eclogites through conditions of Pmax at ca. 690°C–715°C and 36 kbar to Tmax at ca. 710°C–755°C and 18 kbar, prior to extensive re-crystallisation and re-equilibration of these ductile orthogneisses at ca. 400°C–450°C and 6 kbar. The consequential conclusion, that it is no longer necessary to resort to models of tectonic juxtapositioning to explain the spatial association of these Dabieshan orthogneisses with undoubted UHP lithologies, has far-reaching implications for the interpretation of controversial gneiss–eclogite relationships in other UHP metamorphic terrains. 相似文献
16.
Coarse-grained whiteschist, containing the assemblage: garnet+kyanite+phengite+talc+quartz/coesite, is an abundant constituent of the ultrahigh-pressure metamorphic (UHPM) belt in the Kulet region of the Kokchetav massif of Kazakhstan. Garnet displays prograde compositional zonation, with decreasing spessartine and increasing pyrope components, from core to rim. Cores were recrystallized at T=380°C (inner) to 580°C (outer) at P<10 kbar (garnet–ilmenite geothermometry, margarite+quartz stability), and mantles at T=720–760°C and PH20=34–36 kbar (coesite+graphite stability, phengite geobarometer, KFMASH system reaction equilibria). Textural evidence indicates that rims grew during decompression and cooling, within the Qtz-stability field. Silica inclusions (quartz and/or coesite) of various textural types within garnets display a systematic zonal distribution. Cores contain abundant inclusions of euhedral quartz (type 1 inclusions). Inner mantle regions contain inclusions of polycrystalline quartz pseudomorphs after coesite (type 2), with minute dusty micro-inclusions of chlorite, and more rarely, talc and kyanite in their cores; intense radial and concentric fractures are well developed in the garnet. Intermediate mantle regions contain bimineralic inclusions with coesite cores and palisade quartz rims (type 3), which are also surrounded by radial fractures. Subhedral inclusions of pure coesite without quartz overgrowths or radial fractures (type 4) occur in the outer part of the mantle. Garnet rims are silica-inclusion-free. Type 1 inclusions in garnet cores represent the low-P, low-T precursor stage to UHPM recrystallization, and attest to the persistence of low-P assemblages in the coesite-stability field. Coesites in inclusion types 2, 3, and 4 are interpreted to have sequentially crystallized by net transfer reaction (kyanite+talc=garnet+coesite+H2O), and were sequestered within the garnet with progressively decreasing amounts of intragranular aqueous fluid. During the retrograde evolution of the rock, all three inclusion types diverged from the host garnet P–T path at the coesite–quartz equilibrium, and followed a trajectory parallel to the equilibrium boundary resulting in inclusion overpressure. Coesite in type 2 inclusions suffered rapid intragranular H2O-catalysed transformation to quartz, and ruptured the host garnet at about 600°C (when inclusion P27 kbar, garnet host P9 kbar). Instantaneous decompression to the host garnet P–T path, passed through the kyanite+talc=chlorite+quartz reaction equilibrium, resulting in the dusty micro-assemblage in inclusion cores. Type 3 inclusions suffered a lower volumetric proportion transformation to quartz at the coesite–quartz equilibrium, and finally underwent rupture and decompression when T<400°C, facilitating coesite preservation. Type 4 coesite inclusions are interpreted to have suffered minimal transformation to quartz and proceeded to surface temperature conditions along or near the coesite–quartz equilibrium boundary. 相似文献
17.
Based on data on the composition of ore-bearing hydrothermal solutions and parameters of ore-forming processes at various antimony and antimony-bearing deposits, which were obtained in studies of fluid inclusions in ore minerals, we investigated the behavior of Sb(III) in the system Sb–Cl–H 2S–H 2O describing the formation of these deposits. We also performed thermodynamic modeling of native-antimony and stibnite dissolution in sulfide (mHS− = 0.0001−0.1) and chloride (mCl− = 0.1−5) solutions and the joint dissolution of Sb(s)0 and Sb2S3(s) in sulfide-chloride solution (mHS− = 0.01; mCl− = 1) depending on Eh, pH, and temperature. All thermodynamic calculations were carried out using the Chiller computer program. Under the above conditions, stibnite precipitates in acid, weakly acid to neutral, and medium redox solutions, whereas native antimony precipitates before stibnite under more reducing conditions in neutral to alkaline solutions. The metal-bearing capacity of hydrothermal solutions (200–250 °C) of different compositions and origins has been predicted. We have established that the highest capacity is specific for acid (pH = 2–3) high-chloride solutions poor in sulfide sulfur and alkaline (pH = 7–8) low-chloride low-sulfide solutions. 相似文献
18.
Through the analysis of original carbon isotopes in the blocks on the right bank of the Amu Darya River, Turkmenistan, it can be firstly concluded that the carbon dioxide (CO 2) in the sour gas reservoirs belongs to the inorganic-origin gas. The origin of hydrogen sulfide (H 2S) in the Amu Darya Right Bank Block is thermochemical sulfate reduction from the detailed analysis of hydrocarbon source rocks data, reservoir characteristics, vitrinite reflectance of organic matter, and sour gas content. Then, the factors affecting the distribution of sour gases in the Amu Darya Right Bank Block were investigated by the analysis of conventional sour gas distribution factors including geological structure, fracture and fault, caprock integrity, sedimentary facies, reservoir types, lithofacies, the source of sulfur and so on. The following basic findings were achieved: ① The basement rift in the study area is conductive to the distribution of CO 2. The caprock integrity contributes to the concentration of CO 2. The gas reservoirs in the biological dike reefs, patch reefs and overthrust zones usually have medium CO 2 content. ② The geological structure and fracture caused the complexity of the distribution of H 2S. The gypsum-salt rock in upper Jurassic-Tithonian is an important sulphur source, and the main hydrocarbon source rocks are also the major sulfur source of H 2S gas reservoirs. Furthermore, the giant gypsum layers in the middle-upper Jurassic Callovian-Oxfordian and the upper Jurassic-Tithonian are conductive to preservation of H 2S, and the small openings and holes in the reservoir is also correlative to the distribution of H 2S. ③ The H 2S in the study area is mostly distributed in the formations with the geothermal temperature of higher than 100 ℃. The open platform deep-water sedimentary facies are harmful to the formation of H 2S. The patch reef and overthrust zones belong to the belts of low H 2S content, however, the biological dike reef zones belong to the belts of medium-high H 2S content. However, the origin and distribution factors of sour gases in natural gas reservoirs were obtained. At the same time, it was pointed out that more necessary and accurately quantitative research is still needed to determine the origin and distribution of acid gases in the Amu Darya Right Bank Block, Turkmenistan. 相似文献
19.
Metamorphic conditions within arenaceous, calcareous and argillaceous supracrustal rocks of the Magondi Mobile Belt (Zimbabwe) range from greenschist to granulite facies. Within the high-grade segment, basement gneisses of early Proterozoic age and argillaceous rocks of the Mid-Proterozoic Piriwiri Group are intruded by charnockites and enderbites. Metamorphic mineral assemblages and thermobarometric data for enderbitic granulites of Nyaodza show temperatures of 700–800°C and pressures of 5–7 kbar for the peak of granulite-facies metamorphism. Microthermometry and Raman microspectroscopy reveal that CO 2, associated with minor N 2, has been the dominant fluid phase during granulite-facies metamorphism. The chronology of the CO 2 inclusions and the development of microtextures and mineral assemblages in the enderbites indicates that isolated negative crystal shaped CO 2 inclusions in quartz and plagioclase porphyroclasts entrap syn-metamorphic fluids of medium-high densities (0.88–0.90 g/cm 3). Lower density (0.71–0.77 g/cm 3) CO 2 inclusions in trails and clusters within the same minerals were formed from local re-equilibration and re-entrapment of the former (near-) peak granulitic CO 2 inclusions. As in many other granulites, syn-metamorphic CO 2 is associated with intrusives emplaced near the peak of metamorphism. 相似文献
20.
Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM 3+Si 2O 6) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning (K)D(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF 3 limit F content between 6 and 8 GPa. The perovskite KMgF 3 is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. (M4)K-substituted potassic richterite (ideally K(KCa)Mg 5Si 8O 22(OH,F) 2) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H 2O K-cymrite (hydrous hexasanidine–KAlSi 3O 8· nH 2O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H 2O 2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K1−x−n)2(Mg1−nMn3+)2Si2O7H2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H2O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □2Mg2Si2O7H2–(K□)Mg2Si2O7H–K2Mg2Si2O7 (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi3O8, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered. 相似文献
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