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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.
《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   

3.
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   

4.
Carbon isotope thermometry in marbles of the Adirondack Mountains, New York   总被引:4,自引:1,他引:4  
Abstract Carbon isotope thermometry has been applied to coexisting calcite and graphite in marbles from throughout the Adirondack Mountains, New York. Eighty-nine calcite-graphite pairs from the amphibolite grade NW Adirondacks change systematically in temperature north-westwards from 680 to 640 to 670° C over a 30-km distance, reflecting transitions from amphibolite facies towards granulite facies to the north-west and to the south-east. Temperature contours based on calcite-graphite thermometry in the NW Adirondacks parallel mineral isograds, with the orthopyroxene isograd falling above 675° C, and indicate that regional metamorphic temperatures were up to 75° C higher than temperatures inferred from isotherms based on cation and solvus thermometry (Bohlen et al. 1985). Fifty-five calcite-graphite pairs from granulite grade marbles of the Central Adirondacks give regional metamorphic temperatures of 670–780° C, in general agreement with cation and solvus thermometry. Data for amphibolite and granulite grade marbles show a 12%oo range in δ13Ccal and δ13Cgr. A strong correlation between carbon isotopic composition and the abundance of graphite (Cgr/Crock) indicates that the large spread in isotopic compositions results largely from exchange between calcite and graphite during closed system metamorphism. The trends seen in δ13C vs. Cgr/Crock and δ13Ccal vs. δ13Cgr could not have been preserved if significant amounts of CO2-rich fluid had pervasively infiltrated the Adirondacks at any time. The close fit between natural data and calculated trends of δ13C vs. Cgr/Crock indicates a biogenic origin for Adirondack graphites, even though low δ13C values are not preserved in marble. Delamination of 17 graphite flakes perpendicular to the c-axis reveals isotopic zonation, with higher δ13C cores. These isotopic gradients are consistent with new graphite growth or recrystallization during a period of decreasing temperature, and could not have been produced by exchange with calcite on cooling due to the sluggish rate of diffusion in graphite. Samples located >2km from anorthosite show a decrease of 0.5-0.8%oo in the outer 100 μ of the grains, while samples at distances over 8 km show smaller core-to-rim decreases of c.0.2%oo. Correlation between the degree of zonation and distance to anorthosite suggests that the isotopic profiles reflect partial overprinting of higher temperature contact metamorphism by later granulite facies metamorphism. Core graphite compositions indicate contact metamorphic temperatures were 860–890° C within 1 km of the Marcy anorthosite massif. If samples with a significant contact metamorphic effect (Δ(cal-gr) <3.2%oo) are not included, then the remaining 38 granulite facies samples define the relation Δ13C(cal-gr) = 3.56 ± 106T-2 (K).  相似文献   

5.
Ultrahigh-temperature (UHT) metamorphism in the Madurai Block of the southern Indian granulite terrain has been verified using the calcite-graphite isotope exchange thermometer. Carbon isotope thermometry has been applied to marbles from a locality near the reported occurrence of sapphirine granulites that have yielded temperature estimates of around 1000 degrees C. The delta(13)C and delta(18)O values of calcite are homogenous, implying equilibration of the isotopes during metamorphism. However, the delta(13)C values of single graphite crystals show variations in the order of 1 per thousand within a hand specimen. Detailed isotopic zonation studies indicate that graphite preserves either the time-integrated crystal growth history or reequilibrium fractionation during its cooling history. The graphite cores preserve higher delta(13)C values than the rims. The fractionation between calcite and graphite cores gives the highest metamorphic temperature of about 1060 degrees C, which matches the petrologically inferred temperature estimates in the high-magnesian pelites. The fractionation between graphite rims and calcite suggests a temperature of around 750 degrees C, which is interpreted to reflect retrograde cooling. This event is also observed in the sapphirine granulites. Calcite-graphite thermometry thus provides a useful tool to define UHT metamorphism in granulite terrains.  相似文献   

6.
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   

7.
High-temperature, intermediate-pressure calc-silicate marbles occur in the granulite-facies terrain of the La Huerta Range in the Province of San Juan, NW-Argentina, in three bulk-compositional varieties: Type (1) dolomite-absent scapolite-wollastonite-grandite-clinopyroxene-quartz—calcite marbles; Type (2) diopside-forsterite-spinel-corundum—calcite marbles with dolomite exolution lamellae in calcite; Type (3) serpentinized forsterite-spinel-dolomite marbles. An isobaric cooling path from peak-metamorphic conditions of 860°C to 750°C at 6.5 kbar is inferred from scapolite-wollastonite-grandite reaction textures in Type (1) and is consistent with cooling after an advective heat input from related gabbroic and tonalitic intrusive bodies. Stable carbon and oxygen isotope geochemistry was used to decipher the fluid/rock evolution of the three marble types. An interpreted four-stage temperature-time-fluid flow path comprises: (1) infiltration of pre-peak-metamorphic fluids, depleted in δ18O, that caused a shift of primary sedimentary δ18O ratios to lower values (19.6–20.0); (2) syn-metamorphic fluid liberation from Type (1) marbles with evidence for processes close to batch devolatilization that caused a weak coupled 13C and 18O depletion during prograde metamorphism. A different devolatilization behaviour, close to Rayleigh fractionation, texturally associated with fold settings indicates that granulite-facies fluid flow was focused rather than pervasive; (3) H2O-absent conditions were dominant when coronal grandite formed during incipient high-temperature isobaric cooling at the expense of scapolite and wollastonite in the Type (1) marbles; (4) intense post-peak- hydration of Type (2) and Type (3) marbles is the last recognizable metasomatic event. In combination, the three marble types record fluid infiltration both before and after the metamorphic peak.  相似文献   

8.
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   

9.
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   

10.
Graphitization and coarsening of organic material in carbonate-bearing metasedimentary rocks is accompanied by carbon isotope exchange which is the basis of a refractory, pressure-independent geothermometer. Comparison of observed isotopic fractionations between calcite and graphite (δ13CCal–Gr) with independent petrological thermometers provides the following empirical calibration over the range 400–800°C: δ13CCal–Gr= 5.81 times 106×T–2(K) - 2.61. This system has its greatest potential in marbles where calcite + graphite is a common assemblage and other geothermometers are often unavailable. The temperature dependency of this empirical calibration differs from theoretical calibrations; reasons for this are unclear but the new empirical calibration yields temperature estimates in better agreement with independent thermometry from several terranes and is preferred for geological applications. Both calcite-graphite isotopic thermometry and calcite-dolomite solvus thermometry are applied to marble adjacent to the Tudor gabbro in the Grenville Province of Ontario, Canada. The marble has undergone two metamorphic episodes, early contact metamorphism and later regional metamorphism. Values of δ13CCal–Gr decrease regularly from c. 8‰ in samples over 2 km from the pluton to values of 3–4‰ within 200 m of the contact. These samples appear to preserve fractionations from the early thermal aureole with the empirical geothermometer, and indicate temperatures of 450–500° C away from the intrusion and 700–750°C near the gabbro. This thermal profile around the gabbro is consistent with conductive heat flow models. In contrast, the distribution of Mg between calcite and dolomite has been completely reset during later regional metamorphism and yields uniform temperatures of c. 500°C, even at the contact. Graphite textures are important for interpreting the results of the calcite–graphite thermometer. Coarsening of graphite approaching the Tudor gabbro correlates with the decrease in isotopic fractionations and provides textural evidence that graphite crystallization took place at the time of intrusion. In contrast to isotopic exchange during prograde metamorphism, which is facilitated by graphitization, retrogressive carbon isotopic exchange appears to require recrystallization of graphite which is sluggish and easily recognized texturally. Resistance of the calcite–graphite system to resetting permits thermometry in polymetamorphic settings to see through later events that have disturbed other systems.  相似文献   

11.
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   

12.
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   

13.
The In Ouzzal granulitic unit (IOGU) consists predominantly of felsic orthogneisses most of which correspond to granitoids emplaced during the Archaean, plus metasediments, including olivine-spinel marbles, of late Archaean age. All units were metamorphosed at granulite facies during the Eburnean (2 Ga). The stable isotope signature of the marbles (δ13C=–0.8 to –4.2‰/PDB; δ18O = 7.9 to 18.9‰/SMOW) does not record a massive streaming of C-bearing fluids during metamorphism. Most of the isotopic variation in the marbles is explained in terms of pregranulitic features. Metasomatic transformation of granulites into layered potassic syenitic rocks and emplacement of carbonate veins and breccias occurred during retrogressive granulite facies conditions. The chemistry of these rocks is comparable with that of fenites and carbonatites with high contents of (L)REEs, Th, U, F, C, Ba and Sr but, with respect to these elements, a relative depletion in Nb, Ta, Hf, Zr and Ti. The isotopic compositions of Nd (?Nd(T)=–6.3 to –9.9), of Sr (87Sr/86Sr(T)= 0.7093–0.7104), and the O isotopic composition of metasomatic clinopyroxene (δ18O = 6.9 to 8‰), all indicate that the fluid had a strong crustal imprint. On the basis of the C isotope ratios (δ13C =–3.5 to –9.7‰), the fluid responsible for the crystallization of carbonates and metasomatic alteration is thought to be derived from the mantle, presumably through degassing of mantle-derived magmas at depth. Intense interaction with the crust during the upward flow of the fluid may explain its chemical and isotopic signatures. The zones of metasomatic alteration in the In Ouzzal granulites may be the deep-seated equivalents of the zones of channelled circulation of carbonated fluids described at shallower levels in the crust.  相似文献   

14.
The skarn‐type tungsten deposit of the Date‐Nagai mine is genetically related to the granodiorite batholith of the Iidateyama body. Skarn is developed along the contact between pelitic hornfels and marble that remains as a small roof pendant body directly above the granodiorite batholith. Zonal arrangement of minerals is observed in skarn. The zonation consists of wollastonite, garnet, garnet‐epidote, and vesuvianite‐garnet zones, from marble to hornfels. Sheelite is included in garnet, garnet‐epidote, and vesuvianite‐garnet zones. The oxygen isotope values of skarn minerals were obtained as δ18O = 4.2–7.7‰ for garnet, 5.9–6.9‰ for vesuvianite, ?0.3–3.4‰ for scheelite, 6.0–10.9‰ for quartz, and 8.2‰ for muscovite. The temperature of skarn‐formation was calculated from oxygen isotopic values of scheelite‐quartz pairs to be 288°C. Calculated oxygen isotope values of fluid responsible for skarn minerals were 6.1–9.5‰ for garnet, 1.2–4.8‰ for scheelite, ?1.3‐3.6‰ for quartz, and 4.5‰ for muscovite. Garnet precipitated from the fluids of different δ18O values from scheelite, quartz, and muscovite. These δ18O values suggest that the origin of fluid responsible for garnet was magmatic water, while evidence for the presence of a meteoric component in the fluids responsible for middle to later stages minerals was confirmed.  相似文献   

15.
Amphibolite-grade metasediments from the Mgama Hills region, Kenya, contain conspicuous quantities of graphite, most probably derived from organic progenitor materials. The highest graphite contents (5.1–20.4%) are found in schists whereas calcite marbles intercalated in the sequence contain relatively low amounts (0.1–2.0%). The graphitic constituents are consistently enriched in 13C relative to common sedimentary organic material, with the highest isotopic ratios in graphite from the marbles (δ13C = ?7.3 ± 5.0%.; n = 10). Carbon isotope fractionations between calcite and graphite mostly vary between 3.3 and 7.1‰, which comes close to both empirically recorded and thermodynamically calculated fractionations in the temperature range of the upper amphibolite faciès (550–650°C). However, larger values occasionally encountered in the marbles suggest that complete isotopic equilibrium is not always attained in amphibolite-facies metamorphism.  相似文献   

16.
The Mt. Emilius klippe (Western Alps, Italy) corresponds to a segment of the stretched Adriatic continental margin metamorphosed at granulite facies during Permian. This slice was subducted during the early Cenozoic Alpine subduction with the underlying eclogite facies remnants of the Tethyan seafloor (Zermatt‐Saas zone). Near the base of the Mt. Emilius massif, there is a shear zone with eclogite facies hydrofracture systems associated with deformation‐induced re‐equilibration of granulites during high‐P metamorphism. In the basal part of the massif, a pluri‐hectometre domain of sheared mafic boudins is hosted in the granulitic paragneiss. In these mafic boudins, there are garnetites, garnet veins and clinopyroxenites, as well as clinozoisite and calcite veins. These features record multiple events of fracture opening, brecciation, boudinage and parallelization of structures coevally with fluid–rock interaction, metasomatism and volume change. This integrated petrological, micro‐textural and geochemical investigation illustrates the multiplicity and the chemical variability of fluid sources during prograde to peak metamorphic evolution in the lawsonite–eclogite‐facies field (at ~2.15–2.4 GPa, 500–550 °C) during subduction of the Mt. Emilius slice. The calcite veins crosscutting the garnetites have relatively low δ18OVSMOW values (+6.5‰) near those for marble layers (and nearby calcsilicates) embedded within the metasomatized granulites (+8 to +10‰). It is proposed that infiltration of externally‐derived H2O‐rich fluids derived from the plate interface flushed the marbles, promoting decarbonation followed by short‐distance transport and re‐precipitation along garnetite fractures. This study highlights the importance of inherited structural heterogeneities (such as mafic bodies or sills) in localizing deformation, draining fluids from the downgoing plate and creating long‐lasting mechanical instabilities during subduction zone deformation.  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 Whitestone Anorthosite (WSA), located in the Central Gneiss Belt of the south-western Grenville Province, Ontario, exhibits a nearly concentric metamorphic envelope characterized by an increase in modal scapolite, hornblende, epidote and garnet, developed around a core of granulite facies clinopyroxene ± orthopyroxene ± garnet meta-anorthosite. Scapolite- and hornblende-bearing assemblages develop mainly at the expense of plagioclase and pyroxene within the envelope. Stable isotopic and petrological data for scapolite-bearing mineral assemblages within meta-anorthosite constrain the source of carbon responsible for CO3-scapolite formation and the extent of fluid/rock interaction between the anorthosite and adjacent lithologies. Stable isotopic data indicate increasing δ18O and δ13C from core to margin of the meta-anorthosite and for samples from the southern extension of the WSA, where it is ductilely deformed within the Parry Sound Shear Zone (PSSZ). The average δ18OSMOW value (whole rock) for the WSA core is 6.9‰, increasing to 11.5‰ where the WSA is in tectonic contact with marble breccia. The average δ13CPBD value of scapolite in meta-anorthosite from the centre of the WSA is -3.4‰, increasing to -0.5‰ at the eastern (marble) contact. Average values of δ13C for scapolite and whole-rock δ18O for samples from the shear zone are -1.0 and 8.0‰, respectively. Marbles have average δ18O and δ13C values of 19.2 and -0.4‰, respectively. The sulphate content of texturally primary scapolite decreases from the core of the WSA (XSO4= 0.48) to the eastern contact (≤0.05). Texturally late scapolite after plagioclase and garnet tends to be CO3-rich relative to texturally primary scapolite, and some scapolite grains show zoning in the anion site with CO3-enriched rims. Scapolite composition may vary at any scale from a single grain to outcrop. The pattern of isotopic enrichment in 13C and 18O preserved in the eastern margin of the WSA is consistent with marble as the major source of fluid contributing to the formation of the metamorphic envelope. The decrease in XSO4 and increase in XCO3 in scapolite toward the margin of the WSA indicate that the volatile content was reset by, or developed from, a CO2-bearing fluid. Assuming derivation of fluid from marble, minimum fluid/rock values at the margin of the WSA range from 0.03 for the least enriched, to 0.30 for the most isotopically enriched samples. Although marble is not found in immediate contact with samples of sheared meta-anorthosite from the PSSZ, a marble source is also consistent with the C and O isotope composition and anion chemistry of scapolite within these samples.  相似文献   

19.
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   

20.
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   

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