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1.
Carbon and oxygen isotopic profiles around a low pressure metasomatic wollastonite reaction front in a marble of the Hida metamorphic terrain, central Japan, display typical metamorphic fluid-enhanced isotopic zonations. Isotopic profiles obtained from detailed microscale analyses perpendicular to the chemical reaction front in calcite marble show that diffusion-enhanced isotopic exchange may control these profiles. Carbon and oxygen isotopic behaviour in grain boundaries is remarkably different. Oxygen isotopic troughs (18O depleted rims) around the calcite-grain boundaries are widely observed in this contact aureole, demonstrating that diffusion of oxygen in calcite grain boundary dominates over lattice diffusion in calcite. In contrast, no difference is observed in carbon isotopic profiles obtained from grain cores and rims. There is thus no specific role of the grain boundary for diffusion of carbonic species in the metamorphic fluid during transportation. Carbon chemical species such as CO2 and CO3 ions in metamorphic fluid migrate mainly through lattice diffusion. The carbon and oxygen isotope profiles may be modelled by diffusion into a semi-infinite medium. Empirically lattice diffusion of oxygen isotopes is almost six times faster than that of carbon isotopes, and oxygen grain-boundary diffusion is ten times faster than oxygen lattice diffusion. Oxygen isotopic results around the wollastonite vein indicate that migration of the metamorphic fluid into calcite marble was small and was parallel to the aquifer. From the stability of wollastonite and the attainment of oxygen isotopic equilibrium, we suggest that diffusion of oxygen occurred through an aqueous fluid phase. The timescale of formation of the oxygen isotopic profile around the wollastonite vein is calculated to be about 0.76 × 106 years using the experimentally determined diffusion constant. Received: 14 January 1997 / Accepted: 23 April 1998  相似文献   

2.
 The evolution of columnar fiber texture was studied in wollastonite reaction rims synthesized by the reaction calcite + quartz=wollastonite + CO2. Experiments were performed at 850 to 950 °C at 100 MPa in dry CO2 and were evaluated by scanning and transmission electron microscopy. Rim growth rates are interpreted as controlled by the diffusion of the SiO2 component through the rims from the quartz–wollastonite to the wollastonite–calcite interface. The temperature dependence of rim growth rates yields an apparent activation energy of 314 ± 53 kJ mol−1. The columnar fibrous wollastonite crystallizes at the quartz–wollastonite interface and comprises the largest parts of the rims. Ultimately, at the growth front strain contrast centers are present in the quartz. The strained volume extends about 200 nm into the quartz grains. We suggest that this might signify deformation of the quartz lattice due to wollastonite crystallization. Wollastonite fiber thickness was measured from TEM images along traverses that represent intermediate positions of the growth front during the experiments. The average thickness is in the 100–200 nm range. Fiber thickness increases with increasing growth temperature. At a given temperature, the thickness of the fibers at the growth front slightly decreases with time, i.e., the number of fiber tips per unit area in the growth front increases. The decrease of the fiber thickness is well fitted by a parabolic rate law. The generation of the columnar fiber texture is interpreted as an effect of induced stresses at the growth front, resulting from the volume increase due to the local reaction. This volume increase forces SiO2 to diffuse along the growth front to the grain boundaries between the wollastonite fibers. These serve as fast diffusion pathways through the rims. The fiber thickness monitors the diffusion distances in the growth front and thus the height of the induced stress gradients. Since interface reactions are usually associated with volume changes, growth rates of reaction rims and zones in coronas are not only controlled by the diffusive mobility of the components but also by the volume restraints on the interface reactions. Received: 19 July 2002 / Accepted: 14 February 2003  相似文献   

3.
Impure limestones with interstratified metachert layers were contact metamorphosed and metasomatized by the Bufa del Diente alkali syenite. Massive marbles exhibit mineralogical and stable isotope evidence for limited fluid infiltration, confined to a 17 m wide zone at the contact. Influx of magmatic brines along most metacherts produced up to 4 cm thick wollastonite rims, according to calcite (Cc)+quartz (Qz)= wollastonite (Wo)+CO2, and were observed at distances of up to 400 m from the contact. The produced CO2 exsolved as an immiscible low density CO2-rich fluid. Chert protolith isotope compositions were 18O (Qz)=27–30%. and 18O (Cc)=24–27%.. Many wollastonites in infiltrated metacherts have low 18O ranging from 11–17 and confirm that decarbonation occurred in presence of a magmatic-signatured fluid. Large gradients in 18O (Wo) across the rims may reach 6 The 18O of remaining quartz is often lowered to 15–20 whereas caleites largely retained their original compositions. The isotopic reversals of up to 10 between quartz and calcite along with reaction textures demonstrate non-equilibrium between infiltrating fluid in the aquifer and the assemblage calcite+quartz+wollastonite. This is compatible with the assumption of a down-temperature flow of magmatic fluids that occurred exclusively in the remaining quarzite layer. The 13C (Cc) and 18O (Cc) of marble calcites measured perpendicular to two metachert bands reveal significant isotopic alterations along distances of 4.5 cm and 7.5 cm from the wollastonite-marble boundary only into the hanging wall marble, suggesting an advection process caused by a fluid phase which movel upwards. Covariation trends of 13C (Cc) and 18O (Cc) across the alteration front indicate that this fluid was CO2-rich. Mass balance calculations show that all CO2-rich fluid produced by the decarbonation reaction was lost into overlying marble. The metachert aquifers did not leak with respect to water-rich fluids.  相似文献   

4.
Growth rates of wollastonite reaction rims between quartz and calcite were experimentally determined at 0.1 and 1 GPa and temperatures from 850 to 1200 °C. Rim growth follows a parabolic rate law indicating that this reaction is diffusion‐controlled. From the rate constants, the D′δ‐values of the rate‐limiting species were derived, i.e. the product of grain boundary diffusion coefficient D′ and the effective grain boundary width, δ. In dry runs at 0.1 GPa, wollastonite grew exclusively on quartz surfaces. From volume considerations it is inferred that (D′CaOδ)/(D′SiO2δ)≥1.33, and that SiO2 diffusion controls rim growth. D′SiO2δ increases from about 10?25 to 10?23 m3 s?1 as temperature increases from 850 to 1000 °C, yielding an apparent activation energy of 330±36 kJ mol?1. In runs at 1 GPa, performed in a piston‐cylinder apparatus, there were always small amounts of water present. Here, wollastonite rims always overgrew calcite. Rims around calcite grains in quartz matrix are porous and their growth rates are controlled by a complex diffusion‐advection mechanism. Rim growth on matrix calcite around quartz grains is controlled by grain boundary diffusion, but it is not clear whether CaO or SiO2 diffusion is rate‐limiting. D′δ increases from about 10?21 to 10?20 m3 s?1 as temperature increases from 1100 to 1200 °C. D′SiO2δ or D′CaOδ in rims on calcite is c. 10 times larger than D′SiO2δ in dry rims at the same temperature. Growth structures of the experimentally produced rims are very similar to contact‐metamorphic wollastonite rims between metachert bands and limestone in the Bufa del Diente aureole, Mexico, whereby noninfiltrated metacherts correspond to dry and brine‐infiltrated metacherts to water‐bearing experiments. However, the observed diffusivities were 4 to 5 orders of magnitude larger during contact‐metamorphism as compared to our experimental results.  相似文献   

5.
Abstract Granulite facies marbles from the Upper Calcsilicate Unit of the Reynolds Range, central Australia, contain metre-scale wollastonite-bearing layers formed by infiltration of water-rich (XCO2= 0.1–0.3) fluids close to the peak of regional metamorphism at c. 700° C. Within the wollastonite marbles, zones that contain <10% wollastonite alternate on a millimetre scale with zones containing up to 66% wollastonite. Adjacent wollastonite-free marbles contain up to 11% quartz that is uniformly distributed. This suggests that, although some wollastonite formed by the reaction calcite + quartz = wollastonite + CO2, the wollastonite-rich zones also underwent silica metasomatism. Time-integrated fluid fluxes required to cause silica metasomatism are one to two orders of magnitude higher than those required to hydrate the rocks, implying that time-integrated fluid fluxes varied markedly on a millimetre scale. Interlayered millimetre -to centimetre-thick marls within the wollastonite marbles contain calcite + quartz without wollastonite. These marls were probably not infiltrated by significant volumes of water-rich fluids, providing further evidence of local fluid channelling. Zones dominated by grandite garnet at the margins of the marl layers and marbles in the wollastonite-bearing rocks probably formed by Fe metasomatism, and may record even higher fluid fluxes. The fluid flow also reset stable isotope ratios. The wollastonite marbles have average calcite (Cc) δ18O values of 15.4 ± 1.6% that are lower than the average δ18O(Cc) value of wollastonite-free marbles (c. 17.2 ± 1.2%). δ13C(Cc) values for the wollastonite marbles vary from 0.4% to as low as -5.3%, and correlations between δ18O(Cc) and δ13C(Cc) values probably result from the combination of fluid infiltration and devolatilization. Fluids were probably derived from aluminous pegmatites, and the pattern of mineralogical and stable isotope resetting implies that fluid flow was largely parallel to strike.  相似文献   

6.
Quartz–calcite sandstones experienced the reaction calcite+ quartz = wollastonite + CO2 during prograde contact metamorphismat P = 1500 bars and T = 560°C. Rocks were in equilibriumduring reaction with a CO2–H2O fluid with XCO2 = 0·14.The transition from calcite-bearing, wollastonite-free to wollastonite-bearing,calcite-free rocks across the wollastonite isograd is only severalmillimeters wide. The wollastonite-forming reaction was drivenby infiltration of quartz–calcite sandstone by chemicallyreactive H2O-rich fluids, and the distribution of wollastonitedirectly images the flow paths of reactive fluids during metamorphism.The mapped distribution of wollastonite and modeling of an O-isotopeprofile across a lithologic contact indicate that the principaldirection of flow was layer-parallel, directed upward, withany cross-layer component of flow <0·1% of the layer-parallelcomponent. Fluid flow was channeled at a scale of 1–100m by pre-metamorphic dikes, thrust and strike-slip faults, foldhinges, bedding, and stratigraphic contacts. Limits on the amountof fluid, based on minimum and maximum estimates for the displacementof the wollastonite reaction front from the fluid source, are(0·7–1·9) x 105 cm3 fluid/cm2 rock. Thesharpness of the wollastonite isograd, the consistency of mineralthermobarometry, the uniform measured 18O–16O fractionationsbetween quartz and calcite, and model calculations all arguefor a close approach to local mineral–fluid equilibriumduring the wollastonite-forming reaction. KEY WORDS: contact metamorphism, fluid flow, wollastonite, oxygen isotopes, reaction front  相似文献   

7.
The Sr and Pb isotopes from the 31.6 ± 0.3 Ma (2σ) old Diente del Bufa alkali syenite, northeastern Mexico, and marbles of its contact aureole were used to trace the sources and the mobility of these metals during hydrothermal activity. Chert layers form aquifers within the marbles. The marbles represent aquitards. During fluid-wallrock reaction, the chert layers developed wollastonite rims. Early wollastonite rims have Sr and Pb isotopic compositions similar to those of their immediate host marbles, which indicates that the isotopic composition of Sr and Pb is initially buffered by the marble. Later wollastonite and other replacement minerals rimming the aquifer have Sr and Pb isotopic compositions that carry with time increasingly larger contributions from the high-salinity magmatic brine. The Sr and Pb contributions from the alkali syenite can be traced isotopically for more than 90 m away from the contact of the intrusion. In contrast, Sr and Pb originating from the alkali syenite are traceable within the marbles only for 3 to 5 cm from the aquifer-marble boundary. This distance is comparable to the spatial distribution of isotopic alterations of C and O implying that Sr and Pb were transported into the marbles through a fluid phase. The isotopic variation of Sr, Pb, C, and O across the aquifer-marble profiles reflects infiltration as a transport mechanism rather than diffusion. Because Sr and Pb are minor components in both the infiltrating fluid and the rock and because their concentrations are strongly affected by the distribution coefficients among the solid phases present, there is little correlation between the isotopic compositions of the trace elements Sr and Pb and those of C and O, which are major components in fluid and rock. Very thin meta-argillite rinds at the outer margin of the aquifer represent residual material after the dissolution of calcite. They are distinctly enriched in Rb, Sr, and U. The Rb and Sr are to some extent residual from the original limestone mineralogy, whereas U is dominantly derived from the magmatic fluid and leaked from the aquifer with the escaping immiscible CO2-rich H2O-CO2 fluid that was produced by decarbonation. The 238U/204Pb values ranging from 100 to 250 and distinctly lowered Th/U in the meta-argillite rims (1) demonstrate that U was transported with the magmatic fluid along the aquifer and (2) imply that during unmixing of the highly saline magmatic fluid U fractionated into the CO2-rich H2O-CO2 fluid from which it precipitated selectively in the meta-argillite band across the aquifer. Radioautographs demonstrate that the upper meta-argillite rim has 20 to 40 times more U than the lower rim, which implies that 20 to 40 times more CO2-rich H2O-CO2 fluid has left through the upper aquifer contact. Received: 30 September 1997 / Accepted: 15 December 1997  相似文献   

8.
 At the Bufa del Diente contact-metamorphic aureole, brine infiltration through metachert layers embedded in limestones produced thick wollastonite rims, according to Cc+Qz=Wo+CO2. Fluid inclusions trapped in recrystallized quartz hosts include: (1) high salinity four phase inclusions [Th(V-L)=460–573° C; Td(salts)=350–400° C; (Na+K)Cleq=64–73 wt%; X CO 2≤0.02]; (2) low density vapour-rich CO2-bearing inclusions [Th(L-V)≈500±100° C; X CO 2=0.22–0.44; X NaCl≤0.01], corresponding to densities of 0.27± 0.05 gcm−3. Petrographical observations, phase compositions and densities show that the two fluids were simultaneously trapped in the solvus of the H2O-CO2-salts system at 500–600° C and 700±200 bars. The low density fluid was generated during brine infiltration at the solvus via the wollastonite producing reaction. Identical fluid types were also trapped as inclusion populations in wollastonite hosts 3 cm adjacent to quartz crystals. At room temperature, both fluid types additionally contain one quartz and one calcite crystal, generated by the back-reaction Wo+CO2=Cc+Qz of the host with the CO2-proportion of the fluid during retrogression. All of the CO2 was removed from the fluid. On heating in the microstage, the reaction progress of the prograde reaction was estimated via volume loss of the calcites. In vapour-rich fluids, 50% progress is reached at 490–530° C; 80% at 520–560° C; and 100% at 540–590° C, the latter representing the trapping temperatures of the original fluid at the two fluid solvus. The progress is volume controlled. With knowledge of compositions and densities from unmodified inclusions in quartz and using the equation of state of Duan et al. (1995) for H2O-CO2-NaCl, along with f CO 2-values extracted from it, the reaction progress curve was recalculated in the P-T-X-space. The calculated progress curve passes through the two fluid solvus up to 380° C/210 bars, continues in the one fluid field and meets the solvus again at trapping conditions. The P-T slope is steep, most of the reaction occurs above 450° C and there is high correspondence between calculated and measured reaction progress. We emphasize that with the exception of quartz, back-reactions between inclusion fluids and mineral hosts is a common process. For almost any prograde metamorphic mineral that was formed by a devolatilization reaction and that trapped the equilibrium fluid or any peak metamorphic fluid as an inclusion, a fluid-host back-reaction exists which must occur somewhere along the retrograde path. Such retrograde reactions may cause drastic changes in density and composition of the fluid. In most cases, however, evidence of the evolving mineral assemblages is not given for they might form submicroscopical layers at the inclusion walls. Received: 15 March 1995 / Accepted: 1 June 1995  相似文献   

9.
Mid-Proterozoic ( 1000 Ma) granulite facies calc-silicates fromthe Rauer Group, East Antarctica, contain grossular-wollastonite-scapolite-dinopyroxene( + quartz or calcite) assemblages which preserve symplectiteand corona textures typically involving the growth of secondarywollastonite. The textures include (1) wollastonite rims betweenquartz and calcite; (2) wollastonite-plagioclase rims and intergrowthsbetween quartz and scapolite; (3) wollastonite-scapolite-clinopyroxeneinter-growths replacing grossular; and (4) wollastonite-plagioclasesymplectites replacing grossular or earlier symplectites (3). Reactions between grossular, scapolite, wollastonite, calcite,quartz, anorthite, and vapour, have been modelled in the CaO-Al2O3SiO2-H2O-CO2and more complex systems using the internally consistent data-setof Holland & Powell (1990). Reactions producing scapoliteand wollastonite consume vapour as temperature increases (i.e., carbonation), in agreement with the results of Moecher &Essene (1990). These calc-silicates can therefore behave asfluid sinks under high-grade conditions. Conversely, they maybe important fluid sources on cooling and contribute to theformation of post-metamorphic CO2rich fluid inclusions in isobaricallycooled granulites. P-T-CO2 diagrams calculated for typical phase compositions (e.g., garnet, scapolite) demonstrate that the observed texturesare a record of near-isothermal decompression at 800–850 C, consistent with P—rpath determinations based on otherrock types from the Rauer Group. For example, texture (2) resultsfrom crossing the reaction Scapolite + Quartz = Wollastonite + Plagioclase + V on decompression, at 6. 5–7 kb, 820 C, and aCO2 of0–4–0–5. Furthermore, correlations betweenmodes of product phases (e. g., wollastonitexlinopyroxene) andreactant garnet composition preclude open-system behaviour inthe formation of these textures, consistent with post-peak vapour-absentreactions such as Grossular + Calcite + Quartz = Wollastonite + Scapolite occurring on decomposition at high temperatures (>800C). Reaction textures developed in calc-silicates from other granuliteterranes often involve the formation of grossular ( + quartz calcite) as rims on wollastonite-scapolite, or replacementof wollastonite by calcite-quartz. These textures have developedprincipally in response to cooling below 780–810 C andmay be signatures of near-isobaric cooling. Infiltration ofhydrous fluid is not a necessary condition for the productionof garnet coronas in wollastonite-scapolite granulites. *Present address: Department of Earth Sciences, University ofMelbourne, Parkville, Victoria 3052, Australia  相似文献   

10.
Intergranular pressure solution (IPS) is a coupled chemical-mechanical process of widespread importance that occurs during diagenesis and low-temperature deformation of sedimentary rocks. Laboratory experiments on IPS in halite, quartz, and calcite have largely concentrated on the mechanical aspects of the process. In this study, we report the effects of pore fluid chemistry, specifically varying phosphate ion concentration, on the mechanical compaction by IPS of fine-grained calcite powders at room temperature and 1 to 4 MPa applied effective stress. Phosphate was investigated because of its importance as a biogenic constituent of sea and pore waters. Increasing the pore fluid phosphate concentration from 0 to 10−3 mol/L systematically reduced compaction strain rates by up to two orders of magnitude. The sensitivity of the compaction strain rate to phosphate concentration was the same as the sensitivity of calcite precipitation rates to the addition of phosphate ions reported in the literature, suggesting that the rate of IPS in phosphate-bearing samples was controlled by calcite precipitation on pore walls. The results imply that IPS and associated porosity/permeability reduction rates in calcite sediments may be strongly reduced when pore fluids are enriched in phosphates, for example, through high biologic productivity or a seawater origin. Future modeling of IPS-related processes in carbonates must therefore take into account the effects of pore fluid chemistry, specifically the inhibition of interfacial reactions.  相似文献   

11.
The morphologies of calcite grain boundaries were analyzed to provide insight into the evolution of pore networks in unfractured rock. Two synthetic calcite rocks were fabricated by hot isostatically pressing (HIP-ing) dried analytical-grade powders of pure CaCO3 and CaCO3 plus 5% Al2O3 at 600° C and 200 MPa confining pressure for 3 hours (HIP-1). Some samples were HIPed a second time at different temperatures and pressures to investigate the stability of the structures (HIP-2a-c). SEM and TEM were used to image both grain faces and grain boundary cross-sections. Structures on grain faces vary from open shallow basins with peripheral rims, to labyrinths of irregular ridges and channels, to isolated circular depressions. All of these structures are mirrored across the plane between grain faces. The grain size in both the single and two-phase samples increased markedly during HIP-1. Migrating boundaries either dragged pores along or broke away leaving grain interiors dotted with small voids. The structures present after HIP-1 were not stable but evolved considerably in a way dependent on the conditions of the HIP-2. Confining pressure had the most pronounced effect. With low confining pressure, the grain-boundary porosity evolved into isolated circular depressions but the total pore volume did not noticeably decrease. With high confining pressure, the pore volume virtually disappeared. The structures present after HIP-1 are strikingly similar to those that develop in intragranular cracks during healing. We infer that grain boundaries and intragranular cracks heal by similar processes. Decomposition, localized melting, impurities, and anisotropic surface energies played no evident role in forming the grain-boundary structures. The timing of the formation of the porosity and of the subsequent healing processes is more difficult to ascertain. Some structures appear to have evolved gradually throughout the constant, high temperature stage of HIPing. The most obvious structures, however, appear to have evolved on grain boundary cracks that opened during cooling.  相似文献   

12.
Re-equilibration processes of natural H2O–CO2–NaCl-rich fluid inclusions quartz are experimentally studied by exposing the samples to a pure H2O external fluid at 600 °C. Experimental conditions are selected at nearly constant pressure conditions (309 MPa) between fluid inclusions and pore fluid, with only fugacity gradients in H2O and CO2, and at differential pressure conditions (394–398 MPa, corresponding to an internal under-pressure) in addition to similar CO2 fugacity gradients and larger H2O fugacity gradients. Modifications of fluid inclusion composition and density are monitored with changes in ice dissolution temperature, clathrate dissolution temperature and volume fraction of the vapour phase at room temperature. Specific modification of these parameters can be assigned to specific processes, such as preferential loss/gain of H2O and CO2, or changes in total volume. A combination of these parameters can clearly distinguish between modifications according to bulk diffusion or deformation processes. Bulk diffusion of CO2 according to fugacity gradients is demonstrated at constant pressure conditions. The estimated preferential loss of H2O is not in accordance with those gradients in both constant pressure and differential pressure experiments. The development of deformation halos in quartz around fluid inclusions that are either under-pressurized or over-pressurized promotes absorption of H2O from the inclusions and inhibits bulk diffusion according to the applied fugacity gradients.  相似文献   

13.
Hydrothermal alteration of a quartz‐K‐feldspar rock is simulated numerically by coupling fluid flow and chemical reactions. Introduction of CO2 gas generates an acidic fluid and produces secondary quartz, muscovite and/or pyrophyllite at constant temperature and pressure of 300°C and 200 MPa. The precipitation and/or dissolution of the secondary minerals is controlled by either mass‐action relations or rate laws. In our simulations the mass of the primary elements are conserved and the mass‐balance equations are solved sequentially using an implicit scheme in a finite‐element code. The pore‐fluid velocity is assumed to be constant. The change of rock volume due to the dissolution or precipitation of the minerals, which is directly related to their molar volume, is taken into account. Feedback into the rock porosity and the reaction rates is included in the model. The model produces zones of pyrophyllite quartz and muscovite due to the dissolution of K‐feldspar. Our model simulates, in a simplified way, the acid‐induced alteration assemblages observed in various guises in many significant mineral deposits. The particular aluminosilicate minerals produced in these experiments are associated with the gold deposits of the Witwatersrand Basin.  相似文献   

14.
Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO2-H2O fluid compositions of χCO2= 0.61–0.74 in the marbles and χCO2= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO2 diagrams in the model system K2O-CaO-MgO-Al2O3-SiO2-H2O-CO2. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 104 cm3/cm2 and 4.8–12.9 × 104 cm3/cm2, respectively. For an estimated duration of metamorphism of 105 years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10?6 D in the marbles and 10–27 × 10?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.  相似文献   

15.
The 31.6±0.3 Ma old Bufa del Diente alkali-syenite (NE Mexico) intruded a sequence of Cretaceous limestones with intercalated sub-horizontal chert layers. The cherts acted as aquifers that facilitated transport of brines and pegmatitic melts within the shallow-level (<1 kbar) contact-metamorphic aureole. Fluid-driven reactions between chert and marble wallrock, and the influx of late melts and various fluids gave rise to distinct chemical and isotopic signatures within the aquifer and across the zones of infiltration and fluid-driven reaction. Aqueous brines of magmatic origin produced thick wollastonite mantles around the chert layers. Wollastonite formation occurred at the expense of limestone and chert and generated CO2. This CO2-induced fluid unmixing into an aqueous brine and a low-density CO2-rich fluid, which was lost to the overlying marble where it oxidized organic matter and caused 13C and 18O shifts in a zone some 5–10 cm wide. After wollastonite formation, the chert aquifers were locally intruded by pegmatite veins carrying alkali feldspar, quartz, aegirine-augite, eudialyte, zircon, and apatite. Aqueous fluids that exsolved during crystallization of the pegmatite veins escaped along late cross-fractures and migrated along the inner and outer borders of the wollastonite margins. Chemical dispersion patterns of U, Al, Na + K, P, S, Fe, and REE across the chert-to-marble boundary and its metasomatic rims are shown by autoradiography and neutron-induced radiography. Scavenging of cations at mineralogical contacts and cation transport into the marbles occurred only on the mm to cm scale. Isotopic data for Pb and Sr across a simple metachert-marble boundary and for Pb, Sr, Nd, B, and Li across a metachert-pegmatite-marble sequence demonstrate the following: (1) The Pb and Sr isotopic signature of early fluids was buffered by the carbonate wallrock. Only late fluids, shielded from wallrock interaction by a wollastonite mantle, variably preserved a memory of their initial magmatic signature. (2) Since the Nd isotope signature of marble and chert is bound to calcite and clay minerals, systematic shifts to unradiogenic Nd in marble reflect loss of carbonate-bound Nd as the wollastonite margin is approached. Nd in the wollastonite margin is dominated by Nd originally bound to clay minerals. The later emplacement of the pegmatite, which carried the Nd isotope signature of its alkali-syenite source, had little effect on the Nd isotopic composition of the wollastonite rim. (3) Although the Li and B isotopic compositions reflect the alkali-syenite source, they are also affected by isotopic fractionation and partitioning between melt, fluid, and solids.Editorial responsibility J. Hoefs  相似文献   

16.
Fluid compositions and bedding‐scale patterns of fluid flow during contact metamorphism of the Weeks Formation in the Notch Peak aureole, Utah, were determined from mineralogy and stable isotope compositions. The Weeks Formation contains calc‐silicate and nearly pure carbonate layers that are interbedded on centimetre to decimetre scales. The prograde metamorphic sequence is characterized by the appearance of phlogopite, diopside, and wollastonite. By accounting for the solution properties of Fe, it is shown that the tremolite stability field was very narrow and perhaps absent in the prograde sequence. Unshifted oxygen and carbon isotopic ratios in calcite and silicate minerals at all grades, except above the wollastonite isograd, show that there was little to no infiltration of disequilibrium fluids. The fluid composition is poorly constrained, but X(CO2)fluid must have been >0.1, as indicated by the absence of talc, and has probably increased with progress of decarbonation reactions. The occurrence of scapolite and oxidation of graphite in calc‐silicate beds of the upper diopside zone provide the first evidence for limited infiltration of external aqueous fluids. Significantly larger amounts of aqueous fluid infiltrated the wollastonite zone. The aqueous fluids are recorded by the presence of vesuvianite, large decreases in δ18O values of silicate minerals from c. 16‰ in the diopside zone to c. 10‰ in the wollastonite zone, and extensive oxidation of graphite. The carbonate beds interacted with the fluids only along margins where graphite was destroyed, calcite coarsened, and isotopic ratios shifted. The wollastonite isograd represents a boundary between a high aqueous fluid‐flux region on its higher‐grade side and a low fluid‐flux region on its lower‐grade side. Preferential flow of aqueous fluids within the wollastonite zone was promoted by permeability created by the wollastonite‐forming reaction and the natural tendency of fluids to flow upward and down‐temperature near the intrusion‐wall rock contact.  相似文献   

17.
Mineral assemblages, rock and mineral chemistry, and mineral reactions, in calc-silicate rocks from Koduru area, Andhra Pradesh, India are discussed. Mineralogical and bulk chemical differences indicate 3 calc-silicate rock types — type I with K feldspar+calcite+wollastonite+quartz+scapolite+diopsidess +andraditess+sphene, has relatively high rock oxidation ratios. Type II is a highly calcic variety with high rock MgFe ratios, and has K feldspar+calcite+wollastonite+quartz+scapolite + diopsidess±grossularitess+sphene+zoisite. Type III has K feldspar +calcite+wollastonite+quartz+scapolite+diopsidess +sphene+hornblende+magnetite, and has relatively low oxidation ratio and low MgFe ratio. The 3 calc-silicate rock types have originated as mixtures of limestone/dolomite/marl.Diopside was produced by a reaction involving Ca-amphibole +calcite+quartz, and reversed during retrogression. Andraditess in type I rocks was produced at the expense of hedenbergitic component of pyroxene in a continuous reaction as a consequence of increase in the oxygen content of the original sediment relative to type III. Calcite+quartz reacted to give wollastonite. During cooling an influx of water caused scapolite to alter to zoisite.  相似文献   

18.
ABSTRACT With increasing temperature during prograde metamorphism reactions will occur first at the lithological contacts of mixed pelite and calcsilicate terranes. At these interfaces, a fluid of lower chemical potential of H2O and CO2 than that required to produce a fluid in either layer can be produced whether reaction is caused by fluid infiltration or is initially fluid absent. If the interface region does not allow fluid transport then as temperature increases, a fluid pressure greater than lithostatic can develop. At some degree of over-pressure relative to rock pressure, the fluid hydraulically fractures the rock and a gradient in fluid composition away from the contact can be produced. These phenomena occur at the compositional interfaces whenever univariant reactions in the differing layers cross on a temperature vs. mole fraction of CO2 diagram with slopes of opposite sign. The first occurrence of these reaction products at lithological contacts delineates an isograd that defines temperature as well as the mole fraction of CO2 at constant pressure in systems open to fluid transport. These isograds can be contrasted with fluid-producing isograds in closed systems. As an illustration of possible effects, the reactions quartz + clinozoisite + muscovite = anorthite + K-feldspar + H2O and phlogopite + quartz + calcite = tremolite + K-feldspar + H2O + CO2 at 4 kbar are analysed and equations for fluid production and transport are developed.  相似文献   

19.
Calc-silicate boudins from the Rauer Group, East Antarctica, were metamorphosed under granulite facies conditions during late Proterozoic (ca. 1,000 Ma) M3 metamorphism. Boudin cores contain low to moderate aCO 2 assemblages including wollastonite, grossularandradite (grandite) garnet, clinopyroxene, scapolite, plagioclase, quartz±calcite. Petrological and stable isotopic evidence suggests that these core assemblages resulted from pre-peak M3 infiltration of water-rich fluids; there is no evidence for a pervasive fluid phase under peak M3 conditions. The boudins are separated from the surrounding Fe-rich pelites and semi-pelites by a series of concentric, high-variance reaction zones developed under peak M3 conditions. Variations in mineral assemblage, mineral composition and whole rock composition across these zones suggest that they formed by diffusional masstransfer, controlled principally by a chemical potential gradient in Ca across the original calc-silicate-paragneiss lithological boundary. As a consequence of the nearcomplete decarbonation of the calc-silicatesbefore the M3 peak, development of the diffusion-controlled reaction zones did not liberate significant CO2 during granulite facies metamorphism. Similar calcite-poor, low aCO 2 calc-silicate horizons in other granulite facies terrains are unlikely to have been important local fluid sources during deep crustal metamorphism.  相似文献   

20.
Interdiffusion coefficients have been determined for H2O-CO2 mixtures by quantifying the flux of CO2 between two fluid-filled chambers in a specially designed piston-cylinder cell. The two chambers, which are maintained at 1.0 GPa and at temperatures differing by ∼100°C, each contain the XCO2-buffering assemblage calcite + quartz + wollastonite, in H2O. The positive dependence of XCO2 on temperature results in a down-temperature, steady-state flux of CO2 through a capillary tube that connects the two chambers. This flux drives the wollastonite = calcite + quartz equilibrium to the right in the cooler chamber, producing a measurable amount of calcite that is directly related to CO2-H2O interdiffusion rates. Diffusivities calculated from seven experiments range from 1.0 × 10−8 to 6.1 × 10−8 m2/s for mean capillary temperatures between ∼490 and 690°C. The data set can be approximated by an Arrhenius-type relation:
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