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1.
The Valentine wollastonite skarn in the north-west Adirondack Mountains, New York, is a seven million ton deposit which resulted from channellized infiltration of H2O-rich, silica-bearing fluids. The wollastonite formed by reaction of these fluids with non-siliceous calcite marble. The skarn formed at the contact of the syenitic Diana Complex and was subsequently overprinted by Grenville-age granulite facies metamorphism and retrograde hydrothermal alteration during uplift. Calcite marbles adjacent to the deposit have generally high δ18O values (c. 21‰), typical of Grenville marbles which have not exchanged extensively with externally derived fluids. Carbon isotopic fractiona-tions between coexisting calcite and graphite in the marbles indicate equilibration at 675d? C, consistent with the conditions of regional metamorphism. Oxygen isotopic ratios from wollastonite skarn are lower than in the marbles and show a 14‰ variation (-1‰ to 13‰). Some isotopic heterogeneity is preserved from skarn formation, and some represents localized exchange with low-δ18O retrograde fluids. Detailed millimetre- to centimetre-scale isotopic profiles taken across skarn/marble contacts reveal steep δ18O gradients in the skarn, with values increasing towards the marble. The gradients reflect isotopic evolution of the fluid as it reacted with high δ18O calcite to form wollastonite. Calcite in the marble preserves high δ18O values to within <5 mm of the skarn contact. The preservation of high δ18O values in marbles at skarn contacts and the disequilibrium fractionation between wollastonite skarn and calcite marble across these contacts indicate that the marbles were not infiltrated with significant quantities of the fluid. Thus, the marbles were relatively impermeable during both the skarn formation and retrograde alteration. Skarn formation may have been episodic and fluid flow was either chaotic or dominantly parallel to lithological contacts. Although these steep isotope gradients resemble fluid infiltration fronts, they actually represent the sides of the major flow system. Because chromatographic infiltration models of mass transport require the assumption of pervasive fluid flow through a permeable rock, such models are not applicable to this hydrothermal system and, by extension, to many other metamorphic systems where low-permeability rocks restrict fluid migration pathways. Minimum time-integrated fluid fluxes have been calculated at the Valentine deposit using oxygen isotopic mass balance, reaction progress of fluid buffering reactions, and silica mass balance. All three approaches show that large volumes of fluid were necessary to produce the skarn, but silica mass balance calculations yield the largest minimum flux and are hence the most realistic.  相似文献   

2.
Nine marble horizons from the granulite facies terrane of southern India were examined in detail for stable carbon and oxygen isotopes in calcite and carbon isotopes in graphite. The marbles in Trivandrum Block show coupled lowering of δ13C and δ18O values in calcite and heterogeneous single crystal δ13C values (? 1 to ? 10‰) for graphite indicating varying carbon isotope fractionation between calcite and graphite, despite the granulite facies regional metamorphic conditions. The stable isotope patterns suggest alteration of δ13C and δ18O values in marbles by infiltration of low δ13C–δ18O‐bearing fluids, the extent of alteration being a direct function of the fluid‐rock ratio. The carbon isotope zonation preserved in graphite suggests that the graphite crystals precipitated/recrystallized in the presence of an externally derived CO2‐rich fluid, and that the infiltration had occurred under high temperature and low fO2 conditions during metamorphism. The onset of graphite precipitation resulted in a depletion of the carbon isotope values of the remaining fluid+calcite carbon reservoir, following a Rayleigh‐type distillation process within fluid‐rich pockets/pathways in marbles resulting in the observed zonation. The results suggest that calcite–graphite thermometry cannot be applied in marbles that are affected by external carbonic fluid infiltration. However, marble horizons in the Madurai Block, where the effect of fluid infiltration is not detected, record clear imprints of ultrahigh temperature metamorphism (800–1000 °C), with fractionations reaching <2‰. Zonation studies on graphite show a nominal rimward lowering δ13C on the order of 1 to 2‰. The zonation carries the imprint of fluid deficient/absent UHT metamorphism. Commonly, calculated core temperatures are > 1000 °C and would be consistent with UHT metamorphism.  相似文献   

3.
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   

4.
《Gondwana Research》2001,4(3):377-386
The Kerala Khondalite belt is a Proterozoic metasupracrustal granulite facies terrain in southern India comprising garnet-biotite gneiss, garnet-sillimanite gneiss and orthopyroxene granulites as major rock types. Calc-silicate rocks and marbles, occurring as minor lithologies in the Kerala Khondalite Belt, show different mineral assemblages and reaction histories of which indicate a metamorphic P-T-fluid history dominated by internal fluid buffering during the peak metamorphism, followed by external fluid influx during decompression. The carbon and oxygen isotopic compositions of calcite from three representative metacarbonate localities show contrasting evolutionary trends. The Ambasamudram marbles exhibit carbon and oxygen isotope ratios (δ13C ∼ 0‰ and δ18O ∼ 20‰) typical of middle to late Proterozoic marine carbonate sediments with minor variation ascribed to the isotopic exchange due to the devolatilization reactions. The δ13C and δ18O values of ∼ −9‰ and 11‰, respectively, for calcite from calc-silicate rocks at Nuliyam are considerably low and heterogeneous. The wollastonite formation here, possibly corresponds to an earlier event of fluid infiltration during prograde to peak metamorphism, which resulted in decarbonation and isotope resetting. Further, petrologic evidence supports a model of late carbonic fluid infiltration that has partially affected the calc-silicate rocks, with subsequent isotope resetting, more towards the contact between calc-silicate rock and charnockite. At Korani, only oxygen isotopes have been significantly lowered (δ18O ∼ 13‰) and the process involved might be a combination of metamorphic devolatilization accompanied by an aqueous fluid influx, supported by petrologic evidence. The stable isotope signatures obtained from the individual localities, thus indicate heterogeneous patterns of fluid evolution history within the same crustal segment.  相似文献   

5.
The role of volatiles in the stabilization of the lower (granulite facies) crust is contentious. Opposing models invoke infiltration of CO2-rich fluids or generally vapour-absent conditions during granulite facies metamorphism. Stable isotope and petrological studies of granulite facies metacarbonates can provide constraints on these models. In this study data are presented from metre-scale forsteritic marble boudins within Archaean intermediate to felsic orthogneisses from the Rauer Group, East Antarctica. Forsteritic marble layers and associated calcsilicates preserve a range of 13C- and 18O-depleted calcite isotope values (δ13C= -9.9 to -3.0% PDB, δ18O = 4.0 to 12.1% SMOW). A coupled trend of 13C and 18O depletion (～2%, ～5%, respectively) from core to rim across one marble layer is inconsistent with pervasive CO2 infiltration during granulite facies metamorphism, but does indicate localized fluid-rock interaction. At another locality, more pervasive fluid infiltration has resulted in calcite having uniformly low, carbonatite-like δ18O and δ13C values. A favoured mechanism for the low δ18O and δ13C values of the marbles is infiltration by fluids that were derived from, or equilibrated with, a magmatic source. It is likely that this fluid-rock interaction occurred prior to high-grade metamorphism; other fluid-rock histories are not, however, ruled out by the available data. Coupled trends of 13C and 18O depletion are modified to even lower values by the superposed development of small-scale metasomatic reaction zones between marbles and internally folded mafic (?) interlayers. The timing of development of these layers is uncertain, but may be related to Archaean high-temperature (>1000d?C) granulite facies metamorphism.  相似文献   

6.
Abstract Large calcite veins and pods in the Proterozoic Corella Formation of the Mount Isa Inlier provide evidence for kilometre-scale fluid transport during amphibolite facies metamorphism. These 10- to 100-m-scale podiform veins and their surrounding alteration zones have similar oxygen and carbon isotopic ratios throughout the 200 × 10-km Mary Kathleen Fold Belt, despite the isotopic heterogeneity of the surrounding wallrocks. The fluids that formed the pods and veins were not in isotopic equilibrium with the immediately adjacent rocks. The pods have δ13Ccalcite values of –2 to –7% and δ18Ocalcite values of 10.5 to 12.5%. Away from the pods, metadolerite wallrocks have δ18Owhole-rock values of 3.5 to 7%. and unaltered banded calc-silicate and marble wallrocks have δ13Ccalcite of –1.6 to –0.6%, and δ18Ocalcite of 18 to 21%. In the alteration zones adjacent to the pods, the δ18O values of both metadolerite and calc-silicate rocks approach those of the pods. Large calcite pods hosted entirely in calc-silicates show little difference in isotopic composition from pods hosted entirely in metadolerite. Thus, 100- to 500-m-scale isotopic exchange with the surrounding metadolerites and calc-silicates does not explain the observation that the δ18O values of the pods are intermediate between these two rock types. Pods hosted in felsic metavolcanics and metasiltstones are also isotopically indistinguishable from those hosted in the dominant metadolerites and calc-silicates. These data suggest the veins are the product of infiltration of isotopically homogeneous fluids that were not derived from within the Corella Formation at the presently exposed crustal level, although some of the spread in the data may be due to a relatively small contribution from devolatilization reactions in the calc-silicates, or thermal fluctuations attending deformation and metamorphism. The overall L-shaped trend of the data on plots of δ13C vs. δ18O is most consistent with mixing of large volumes of externally derived fluids with small volumes of locally derived fluid produced by devolatilization of calc-silicate rocks. Localization of the vein systems in dilatant sites around metadolerite/calc-silicate boundaries indicates a strong structural control on fluid flow, and the stable isotope data suggest fluid migration must have occurred at scales greater than at least 1 km. The ultimate source for the external fluid is uncertain, but is probably fluid released from crystallizing melts derived from the lower crust or upper mantle. Intrusion of magmas below the exposed crustal level would also explain the high geothermal gradient calculated for the regional metamorphism.  相似文献   

7.
Vein-controlled retrograde infiltration of H2O-CO2 fluids into Dalradian epidote amphibolite facies rocks of the SW Scottish Highlands under greenschist facies conditions resulted in alteration of calcite-rich marble bands to dolomite and spatially associated 18O enrichment of about 10%. on a scale of metres. Fluid inclusion data indicate that the retrograde fluid was an H2O-salt mixture with a low CO2 content, and that the temperature of the fluid was about 400d? C. Detailed petrographic and textural (backscattered electron imaging) studies at one garnet-grade locality show that advection of fluid into marbles proceeded by a calcite-calcite grain edge flow mechanism, while alteration of non-carbonate wall-rock is associated with veinlets and microcracks. Stable isotopic analysis of carbonates from marble bands provides evidence for advection of isotopic fronts through carbonate wall-rocks perpendicular to dolomite veins, and fluid fluxes in the range 2.4–28.6 m3/m2 have been computed from measured advection distances. Coincidence of isotope and reaction fronts is considered to result from reaction-enhanced kinetics of isotope exchange at the reaction front. Front advection distances are related to the proportion of calcite to quartz in each marble band, with the largest advection distance occurring in nearly pure calcite matrix. This relationship indicates that fluid flow in carbonates is only possible along fluid-calcite-calcite grain edges. However, experimental constraints on dihedral angles in calcite-fluid systems require that pervasive infiltration occurred in response to calcite dissolution initiated at calcite-calcite grain junctions rather than to an open calcite pore geometry. The regional extent of the retrograde infiltration event has been documented from the high δ18O of dolomite-ankerite carbonates from veins and host-rocks over an area of least 50 × 50 km in the SW Scottish Highlands. Isotopically exotic 18O-rich retrograde fluids have moved rapidly upwards through the crust, inducing isotopic exchange and mineral reaction in wall-rocks only where lithology, pore geometry or mineral solubilities, pressure and temperature have been appropriate for pervasive infiltration to occur.  相似文献   

8.
At Naxos, Greece, a migmatite dome is surrounded by schists and marbles of decreasing metamorphic grade. Sillimanite, kyanite, biotite, chlorite, and glaucophane zones are recognized at successively greater distances from the migmatite dome. Quartz-muscovite and quartz-biotite oxygen isotope and mineralogie temperatures range from 350 to 700°C.The metamorphic complex can be divided into multiple schist-rich (including migmatites) and marblerich zones. The δ18O values of silicate minerals in migmatite and schist units and quartz segregations in the schist-rich zones decrease with increase in metamorphic grades. The calculated δ18OH2O values of the metamorphic fluids in the schist-rich zones decrease from about 15‰ in the lower grades to an average of about 8.5‰ in the migmatite.The δD values of OH-minerals (muscovite, biotite, chlorite, and glaucophane) in the schist-rich zones also decrease with increase in grade. The calculated δDH2O values for the metamorphic fluid decrease from ?5‰ in the glaucophane zone to an average of about ?70‰ in the migmatite. The δD values of water in fluid inclusions in quartz segregations in the higher grade rocks are consistent with this trend.Theδ18O values of silicate minerals and quartz segregations in marble-rich zones are usually very large and were controlled by exchange with the adjacent marbles. The δD values of the OH minerals in some marble-rich zones may reflect the value of water contained in the rocks prior to metamorphism.Detailed data on 20 marble units show systematic variations of δ18O values which depend upon metamorphic grade. Below the 540°C isograd very steep δ18O gradients at the margins and large δ18O values in the interior of the marbles indicate that oxygen isotope exchange with the adjacent schist units was usually limited to the margins of the marbles with more exchange occurring in the stratigraphic bottom than in the top margins. Above the 540°C isograd lower δ18O values occur in the interior of the marble units reflecting a greater degree of recrystallization and the occurrence of Ca-Mg-silicates.Almost all the δ13C values of the marbles are in the range of unaltered marine limestones. Nevertheless, the δ13C values of most marble units show a general correlation with δ18O values.The CO2H2O mole ratio of fluid inclusions in quartz segregations range from 0.01 to 2. Theδ13C values of the CO2 range from ?8.0 to 3.6‰ and indicate that at some localities CO2 in the metamorphic fluid was not in carbon isotopic equilibrium with the marbles.  相似文献   

9.
Stable-isotope profiles show that flat-lying marble units acted as impermeable barriers to upward fluid flow in transitional amphibolite-granulite grade rocks of the Kigluaik Mountains, Seward Peninsula, Alaska. The degree of permeability is related to the composition of the marble. The margin of a thick pure dolomite marble chemically reacted with underlying metasyenite (aH2O=0.2) to form a 2 cm boundary layer of calcite + forsterite by introduction of SiO2. No fluid penetrated past this reaction front, although the high temperature of metamorphism (800°C) allowed transport of carbon and oxygen isotopes for an additional 2 cm by diffusion through the solid dolomite. A second marble with a higher silica content underwent more decarbonation, which enhanced porosity and lead to a greater extent of isotope transport (2–3 m) in contact with quartzo-feld-spathic gneiss below. An estimate of total fluid flux across the bottom of this marble layer based on the shape of the isotope profile is 1 cm3/cm2 directed down, out of the marble. At two other marble-gneiss contacts steep isotopic gradients coincide with lithologic contacts, indicating very little cross-lithology fluid flow. The extent of diffusional transport of isotopes in the marbles is limited and interpreted as indicating the transient presence of a pore fluid, generated by thermally driven devolatilization reactions. No wholesale pervasive advection of C-O-H fluid occurred across the thick, continuous, marble units near the exposed base of the Kigluaik Group section during the entire regional metamorphic cycle. Activities of pore-fluid species were controlled by internal processes. Movement of volatiles and stable-isotopes between contrasting rock-types was dominantly diffusive. Channelized fluid pathways through the marble units developed during uplift and cooling but were not present during peak metamorphism. Heating of the section occurred by conduction, probably from an underlying magma source, and not by advection of a C-O-H fluid.  相似文献   

10.
Nineteen samples of metamorphosed carbonate-bearing rocks were analyzed for carbon and oxygen isotope ratios by ion microprobe with a ∼5-15 μm spot, three from a regional terrain and 16 from five different contact aureoles. Contact metamorphic rocks further represent four groups: calc-silicate marble and hornfels (6), brucite marble (2), samples that contain a reaction front (4), and samples with a pervasive distribution of reactants and products of a decarbonation reaction (4). The average spot-to-spot reproducibility of standard calcite analyses is ±0.37‰ (2 standard deviations, SD) for δ18O and ±0.71‰ for δ13C. Ten or more measurements of a mineral in a sample that has uniform isotope composition within error of measurement can routinely return a weighted mean with a 95% confidence interval of 0.09-0.16‰ for δ18O and 0.10-0.29‰ for δ13C. Using a difference of >6SD as the criterion, only four of 19 analyzed samples exhibit significant intracrystalline and/or intercrystalline inhomogeneity in δ13C at the 100-500 μm scale, with differences within individual grains up to 3.7‰. Measurements are consistent with carbon isotope exchange equilibrium between calcite and dolomite in five of six analyzed samples at the same scale. Because of relatively slow carbon isotope diffusion in calcite and dolomite, differences in δ13C can survive intracrystalline homogenization by diffusion during cooling after peak metamorphism and likely represent the effects of prograde decarbonation and infiltration. All but 2 of 11 analyzed samples exhibit intracrystalline differences in δ18O (up to 9.4‰), intercrystalline inhomogeneity in δ18O (up to 12.5‰), and/or disequilibrium oxygen isotope fractionations among calcite-dolomite, calcite-quartz, and calcite-forsterite pairs at the 100-500 μm scale. Inhomogeneities in δ18O and δ13C are poorly correlated with only a single mineral (dolomite) in a single sample exhibiting both. Because of relatively rapid oxygen isotope diffusion in calcite, intracrystalline inhomogeneities in δ18O likely represent partial equilibration between calcite and fluid during retrograde metamorphism. Calcite is in oxygen isotope exchange equilibrium with forsterite in one of four analyzed samples, in equilibrium with dolomite in none of six analyzed samples, and in equilibrium with quartz in neither of two analyzed samples. There are no samples of contact metamorphic rock with analyzed reactants and products of an arrested metamorphic reaction that are in oxygen isotope equilibrium with each other. The degree of departure from equilibrium in analyzed samples is variable and is often related, at least in part, to alteration of δ18O of calcite during retrograde fluid-rock reaction. In situ sub-grain-scale carbon and oxygen isotope analyses of minerals are advisable in the common applications of stable isotope geochemistry to metamorphic petrology. Correlation of sub-mm scale stable isotope data with imaging will lead to improved understanding of reaction kinetics, reactive fluid flow, and thermal histories during metamorphism.  相似文献   

11.
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   

12.
The primary occurrence of ruby in the Mogok area, northern Myanmar is exclusively found in marble along with spinel–forsterite-bearing marble and phlogopite–graphite marble. These marble units are enclosed within banded biotite–garnet–sillimanite–oligoclase gneisses. Samples of these marbles collected for C–O stable isotope analysis show two trends of δ13C–δ18O variation resulting most likely from fluid–rock interactions. Ruby-bearing marble and phlogopite–graphite marble follow a trend with coupled C–O depletion, whereas spinel–forsterite-bearing marble follows a δ18O depletion trend with relatively constant δ13C values. Ruby formation might have resulted from CO2-rich fluid–rock interaction, while spinel–forsterite-bearing marble was genetically related to CO2-poor fluid–rock interaction. Both fluids may have arisen from external sources. Based on graphite Raman spectral thermometry, the estimated temperature for phlogopite–graphite marble, and probably ruby-bearing marble, was lower than 607 °C, and for spinel–forsterite-bearing marble, lower than 710 °C. Contrasting C/O diffusion between graphite/ruby/spinel/forsterite and calcite, local variations of isotopic compositions of newly formed minerals as a result of non-pervasive fluid infiltration, and open-system isotopic disturbance during cooling may have affected C-/O-isotopic fractionations between minerals. The estimated high formation temperatures for ruby and spinel/forsterite imply that the parental fluids may have been related to nearby igneous intrusions and/or metamorphic processes. Whether these two types of fluid were genetically related is unclear based on the present data.  相似文献   

13.
 Late Proterozoic to Cambrian carbonate rocks from Lone Mountain, west central Nevada, record multiple post-depositional events including: (1) diagenesis, (2) Mesozoic regional metamorphism, (3) Late Cretaceous contact metamorphism, related to the emplacement of the Lone Mountain granitic pluton and (4) Tertiary hydrothermal alteration associated with extension, uplift and intrusion of silicic porphyry and lamprophyre dikes. Essentially pure calcite and dolomite marbles have stable isotopic compositions that can be divided into two groups, one with positive δ13C values from+3.1 to +1.4 ‰ (PDB) and high δ18O values from +21.5 to +15.8 ‰ (SMOW), and the other with negative δ13C values from –3.3 to –3.6‰ and low δ18O values from +16.9 to +11.1‰. Marbles also contain minor amounts of quartz, muscovite and phlogopite. Brown and blue luminescent, clear, smooth textured quartz grains from orange luminescent calcite marbles have high δ18O values from +23.9 to +18.1‰, while brown luminescent, opaque, rough textured quartz grains from red luminescent dolomite marbles typically have low δ18O values from +2.0 to +9.3‰. The δ18O values of muscovite and phlogopite from marbles are typical of micas in metamorphic rocks, with values between +10.4 and +14.4‰, whereas mica δD values are very depleted, varying from −102 to −156‰. No significant lowering of the δ18O values of Lone Mountain carbonates is inferred to have occurred during metamorphism as a result of devolatilization reactions because of the essentially pure nature of the marbles. Bright luminescence along the edges of fractures, quartz cements and quartz overgrowths in dolomite marbles, low δD values of micas, negative δ13C values and low δ18O values of calcite and dolomite, and depleted δ18O values of quartz from dolomite marbles all indicate that meteoric fluids interacted with Lone Mountain marbles during the Tertiary. Partial oxygen isotopic exchange between calcite and low 18O meteoric fluids lowered the δ18O values of calcite, resulting in uniform quartz-calcite fractionations that define an apparent pseudoisotherm. These quartz-calcite fractionations significantly underestimate both the temperature of metamorphism and the temperature of post-metamorphic alteration. Partial oxygen isotopic exchange between quartz and meteoric fluids also resulted in 18O depletion of quartz from dolomite marbles. This partial exchange was facilitated by an increase in the surface area of the quartz as a result of its dissolution by meteoric fluids. The negative δ13C values in carbonates result from the oxidation of organic material by meteoric fluids following metamorphism. Stable isotopic data from Lone Mountain marbles are consistent with the extensive circulation of meteoric hydrothermal fluids throughout western Nevada in Tertiary time. Received: 1 February 1994/Accepted: 12 September 1995  相似文献   

14.
An extensive humite‐bearing marble horizon within a supracrustal sequence at Ambasamudram, southern India, was studied using petrological and stable isotopic techniques to define its metamorphic history and fluid characteristics. At peak metamorphic temperatures of 775±73°C, based on calcite‐graphite carbon isotope thermometry, the mineral assemblages suggest layer‐by‐layer control of fluid compositions. Clinohumite + calcite‐bearing assemblages suggest XCO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest XCO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at XCO2 of c. 0.3. Retrograde reaction textures such as scapolite + quartz symplectites after feldspar and calcite and replacement of dolomite + diopside or tremolite+dolomite after calcite+forsterite or calcite+clinohumite are indicative of retrogression under high XCO2 conditions. Calcite preserves late Proterozoic carbon and oxygen isotopic signatures and the marble lacks evidence for extensive retrograde fluid infiltration, while during prograde metamorphism the possible infiltration of aqueous fluids did not produce significant isotopic resetting. Isotopic zonation of calcite and graphite grains was likely produced by localized CO2 fluid infiltration during retrogression. Contrary to the widespread occurrence of humite‐marbles related to retrograde aqueous fluid infiltration, the Ambasamudram humite‐marbles record a prograde‐to‐peak metamorphic humite formation and retrogression under conditions of low XH2O.  相似文献   

15.
18O/16O ratios vary systematically in the 1,000 m section of interlayered metasediments and granitoids at Lizzies Basin, the deepest structural level exposed in the East Humboldt Range metamorphic core complex. In the lower 300 m of the section (the Lower Zone) 18O is homogeneous and low (+6.6 to +8.8 in silicate rocks, +8.7 to +12.1 in marbles). A detailed oxygen isotope profile across an individual marble layer within the Lower Zone has a similar range in 18O (+9.5 to +11.9) with the highest values preserved in the middle of the layer. In the upper 700 m of the section (the Upper Zone) metasediments have been less strongly 18O depleted. The 18O values are higher and more heterogeneous and in a profile across a marble layer of similar thickness, rise steeply from marginal values of +12 to core values of +23. Quartz from silicate metasediments throughout the Upper Zone ranges from +11 to +13 and is thus fairly homogeneous, particularly where detailed profiles have been measured adjacent to the 18O-rich marble layers. Covariation of 18O/16O and 13C/12C ratios in marbles suggests that the isotopic composition of these elements has been altered by exchange with infiltrating, water-rich, CO2–H2O fluids with mantle-like isotopic composition. In most cases, marble cores preserve protolith 13C values and these vary systematically throughout the section according to structural level, including some exceptionally 13C-rich values up to +12. This range may reflect stratigraphic variation in 13C of the Proterozoic sedimentary protoliths of these rocks. The Upper/Lower Zone boundary, and the contrast in isotope systematics to either side, has been previously explained either as an impermeable barrier to fluid flow, or as an infiltration front (Wickham and Peters 1990). The second alternative has been tested using a numerical model in which low-18O aqueous fluid flows vertically upward through an alternating sequence of monomineralic quartz (18O=+12) and calcite (18O=+22) layers in a regime in which the oxygen isotopic composition is controlled by advection, diffusion (in the fluid), and fluid/solid exchange. Solutions to the relevant transport equations indicate that the abrupt change in the average 18O value of the layers at the Upper/Lower Zone boundary can be reproduced by the model with a uniform porosity throughout the system, but the observed contrast in the shapes of the marble layer profiles in the Upper and Lower Zones cannot be reproduced under these conditions. However, if the calcite layers have two orders of magnitude lower porosity in comparison with the quartz layers and exchange within them is diffusion-dominated (as opposed to advection-dominated in the quartz) the contrasting shapes of the marble profiles in the two zones are reproduced, as well as the Upper/Lower Zone discontinuity. The range of conditions that generates both an infiltration front (at the appropriate scale) and contrasting marble profiles (at the appropriate scale) is quite narrow but requires a volatile flux that could be generated by plausible volumes of mantle-derived magma crystallizing at depth beneath the area, providing support for this mechanism as a viable agent of 18O depletion in the deep-level rocks of this terrane.  相似文献   

16.
Carbon isotope fractionations between calcite and graphite in the Panamint Mountains, California, USA, demonstrate the importance of mass balance on carbon isotope values in metamorphosed carbon-bearing minerals while recording the thermal conditions during peak regional metamorphism. Interbedded graphitic marbles and graphitic calcareous schists in the Kingston Peak Formation define distinct populations on a δ13C(gr)–δ13C(cc) diagram. The δ13C values of both graphite and calcite in the marbles are higher than the values of the respective minerals in the schists. δ13C values in both rock types were controlled by the relative proportions of the carbon-bearing minerals: calcite, the dominant carbon reservoir in the marble, largely controlled the δ13C values in this lithology, whereas the δ13C values in the schists were largely controlled by the dominant graphite. This is in contrast to graphite-poor calcsilicate systems where carbon isotope shifts in carbonate minerals are controlled by decarbonation reactions. The marbles record a peak temperature of 531±30 °C of a Jurassic low-pressure regional metamorphic event above the tremolite isograd. In the schists there is a much wider range of recorded temperatures. However, there is a mode of temperatures at c. 435 °C, which approximately corresponds to the temperatures of the principal decarbonation metamorphic reactions in the schists, suggesting that the carbon exchange was set by loss of calcite and armouring of graphite by newly formed silicate minerals. The armouring may explain the relatively large spread of apparent temperatures. Although the modal temperature also corresponds to the approximate temperature of the Cretaceous retrograde event, retrograde exchange is thought less likely due to very slow exchange rates involving well-crystallized graphite, armouring of graphite by silicates during the earlier event, and because of other barriers to retrograde carbon exchange. Thus, only the calcite–graphite carbon isotope fractionations recorded by the marbles demonstrate the high-temperature conditions of the low-pressure Jurassic metamorphic event that was associated with the emplacement of granitic plutons to the west of the Panamint Mountains.  相似文献   

17.
The intracrystalline diffusion rate of oxygen in diopside was constrained based on natural isotopic variations from a granulite facies marble from Cascade Slide, Adirondacks (New York, USA). The oxygen isotope compositions of the diopsides, measured as a function of grain size, are nearly constant (20.9 ± 0.3‰ vs. SMOW) over the entire measured size range (0.3–3.2 mm diameter). The δ18O values of the cores of calcite grains are 23.0‰. Temperature estimates based on the Δ18O(calcite-diopside) are 800d?C, in agreement with the highest previous thermometric estimates for these rocks. The lack of isotopic variation in the diopsides as a function of grain size requires that the oxygen intracrystalline diffusion rate in diopside from the Adirondack samples was very slow. The maximum diffusion rates (D800d?C parallel to the c-axis) were calculated with an infinite reservoir model (IRM) and a finite reservoir model (FRM) that incorporates mineral modal abundances and initial isotopic variations. For an assumed activation energy (Q) = 100 kJ/mol, the IRM diffusion rate estimate of 1.6 times 10-20cm2/s is two orders of magnitude faster than from the FRM; at Q=500kJ/mol, the D800d?C estimate for both methods is c. 5.6 times 10-20 cm2/s. The present results require that a hydrothermal fluid significantly enhances the diffusion rate of oxygen in diopside if previous data are correct. The δ18O(SMOW) and δ13C(PDB) values of the calcite, measured in situ with a CO2 laser, are 22.9 ± 0.3, 0.1±0.3‰ in the grain cores, 22.1 ±0.3, 0.2 ±0.1‰ at the grain boundaries and 21.7 ±0.4, -0.6±0.1‰ abutting diopside grains. The δ18O and δ13δC values measured conventionally are: crystal cores, 22.96, -0.95‰; abutting diopside grains, 22.38, -0.93‰; bulk, 22.79, -0.95%. Use of the bulk δ18O(calcite) values for thermometry yields unreasonably high temperatures. The lower δ18O values at the calcite grain boundaries are not due to retrograde diffusional exchange with the diopside, they are thought to be a result of a late retrograde fluid infiltration.  相似文献   

18.
The Vil-car-1 flowstone core from Villars cave (SW France) provides one of the first European speleothem records extending back to 180 ka, based on U–Th TIMS and MC-ICP-MS measurements. The core offers a continuous record of Termination II and the Last Interglacial. The penultimate deglaciation is characterized by a prominent 5‰ depletion in calcite δ18O. Determining which specific environmental factors controlled such a large oxygen isotopic shift offers the opportunity to assess the impact of various factors influencing δ18O variations in speleothem calcite.Oxygen isotope analyses of fluid inclusions indicate that drip water δ18O remained within a very narrow range of ±1‰ from Late MIS6 to the MIS5 δ18O optimum. The possibility of such a stable behaviour is supported by simple calculations of various effects influencing seepage water δ18O.Although this could suggest that the isotopic shift in calcite is mainly driven by temperature increase, attempts to quantify the temperature shift from Late MIS6 to the MIS5 δ18O optimum by assuming an equilibrium relationship between calcite and fluid inclusion δ18O yield unreasonably high estimates of ～20 °C warming and Late MIS6 cave temperatures below 0 °C; this suggests that the flowstone calcite precipitated out of thermodynamic equilibrium at this site.Using a method proposed by Guo et al. (submitted for publication) combining clumped isotope measurements, fluid inclusion and modern calcite δ18O analyses, it is possible to quantitatively correct for isotopic disequilibrium and estimate absolute paleotemperatures. Although the precision of these absolute temperature reconstructions is limited by analytical uncertainties, the temperature rise between Late MIS6 and the MIS5 optimum can be robustly constrained between 13.2 ± 2.6 and 14.6 ± 2.6 °C (1σ), consistent with existing estimates from Western Europe pollen and sea-surface temperature records.  相似文献   

19.
 Siliceous dolomites and limestones contain abundant retrograde minerals produced by hydration-carbonation reactions as the aureole cooled. Marbles that contained periclase at the peak of metamorphism bear secondary brucite, dolomite, and serpentine; forsterite-dolomite marbles have retrograde tremolite and serpentine; wollastonite limestones contain secondary calcite and quartz; and wollastonite-free limestones have retrograde tremolite. Secondary tremolite never appears in marbles where brucite has replaced periclase or in wollastonite-bearing limestones. A model for infiltration of siliceous carbonates by CO2-H2O fluid that assumes (a) vertical upwardly-directed flow, (b) fluid flux proportional to cooling rate, and (c) flow and reaction under conditions of local equilibrium between peak temperatures and ≈400 °C, reproduces the modes of altered carbonate rocks, observed reaction textures, and the incompatibility between tremolite and brucite and between tremolite and wollastonite. Except for samples from a dolomite xenolith, retrograde time-integrated flux recorded by reaction progress is on the order of 1000 mol fluid/cm2 rock. Local focusing of flow near the contact is indicated by samples from the xenolith that record values an order of magnitude greater. Formation of periclase, forsterite, and wollastonite at the peak of metamorphism also required infiltration with prograde time-integrated flux approximately 100–1000 mol/cm2. The comparatively small values of prograde and retrograde time-integrated flux are consistent with lack of stable isotope alteration of the carbonates and with the success of conductive thermal models in reproducing peak metamorphic temperatures recorded by mineral equilibria. Although isobaric univariant assemblages are ubiquitous in the carbonates, most formed during retrograde metamorphism. Isobaric univariant assemblages observed in metacarbonates from contact aureoles may not record physical conditions at the peak of metamorphism as is commonly assumed. Received: 19 September 1995 / Accepted: 14 March 1996  相似文献   

20.
This work deals with structural and geochemical (chemical and isotopic) analyses of calcite veins hosted in Carrara marbles in the Alpi Apuane, NW Tuscany, Italy. Geometric features and spatial distribution of veins provided estimations of stress ratio (Φ = (σ2 − σ3)/(σ1 − σ3)), driving stress ratio (R′ = (Pf − σ3)/(σ1 − σ3)) and fluid overpressure (Δsi = Pf − σ3) at the time of vein formation. The obtained values of Φ = 32 and R′ = 0.43 reveal that fluid pressure was higher than the intermediate principal stress at the time of veins formation, whereas the estimated Δsi ranging from 129 to 207 MPa indicates that veins formed under supra-hydrostatic to lithostatic pressure conditions. Carbon (δ13CV-PDB = 1.81–2.10‰ for veins and 1.95–2.51‰ for host marbles), oxygen (δ18OV-SMOW = 28.71–29.57‰ for veins and 28.90–29.36‰ for host marbles) and strontium (87Sr/86Sr = 0.707716–0.707985 for veins and 0.0707708–0.707900 for host marbles) isotope compositions in vein/host marble pairs were internally quite consistent. Combining our structural and geochemical data, a modeling approach was performed to investigate the compositional features and temperatures of calcite depositing fluids. The results of our studies give evidence that (1) pore-fluids in Carrara marble, consisting of metamorphic formation waters, were re-mobilized during veining event and migrated within the veins in closed system conditions, (2) veins formed after ductile folding phases and before high-angle brittle faulting events, at temperature and pressure around 250 °C and 210 MPa, and finally (3) about 12 g H2O/m3 marble are calculated to have been available as vein parental fluid at the time of vein formation.  相似文献   

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