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1.
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   

2.
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   

3.
《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   

4.
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   

5.
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   

6.
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   

7.
The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO2-H2O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks.Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed.Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in 18O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences.The range of Adirondack carbonate 18O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor 18O and 13C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their premetamorphic isotopic compositions. Such preservation is particularly evident in instances of high 18O calcites (25.0 to 27.2), low 18O wollastonites (–1.3 to 3.5), and sharp gradients in 18O (18 permil/15m between marble and anorthosite, 8 permil/25 m in metasediments, and 6 permil/1 m in skarn).Isotopic exchange is seen across marble-anorthosite and marble-granite contacts only at the scale of a few meters. Small (<5 m) marble xenoliths are in approximate exchange equilibrium with their hosts, but for larger xenoliths and layers of marble there is no evidence of exchange at distances greater than 10 m from meta-igneous contacts.  相似文献   

8.
Grandite garnet-rich calcsilicate rocks from the Lower Calcsilicate Unit of the regionally metamorphosed Reynolds Range Group (central Australia) crop out along a strike-parallel section in which a transition zone from M22 amphibolite to granulite facies rocks is exposed. Across this transition the grandite-rich layers do not show systematic changes in mineral assemblages, compositions and modes, or stable isotope compositions. These layers are deformed by F22 folds that are associated with the peak of regional low-pressure/high-temperature metamorphism. Therefore, the grandite-rich layers appear to pre-date regional metamorphism and to have acted as closed chemical systems during prograde M22 metamorphism. Mineral assemblages in the grandite-rich layers are consistent with their formation through the infiltration of oxidized, water-rich fluids (Xco2 < 0.1–0.3; log fo2 -16 to -14). The stable isotope values of calcite (Δ13C=-4.2 to -0.8%0 PDB; Δ18O = 10.5–14.0%0 V-SMOW) and bulk-silicate fractions (Δ18O = 6.1 to 10.8%) of the grandite-rich layers are most consistent with the infiltrating fluid being from a magmatic source. It is most likely that fluid infiltration occurred during the pre-M22 contact metamorphism (M21) that affected much of the Reynolds Range Group. The preservation of these assemblages is probably due to their high variance and little pervasive fluid-rock interaction having occurred during M22. The clinopyroxene- and feldspar-rich calcsilicate rocks that host the grandite-rich layers contain poikiloblastic grandite garnet that formed during prograde M22 metamorphism. Thin marbles that locally occur with the grandite-rich layers contain a third garnet generation that is post- or late M22. This grossular-rich garnet occurs in coronas around calcite, plagioclase, clinopyroxene, wollastonite and scapolite. These coronas are consistent with cooling and/or compression. However, because the marble assemblages are themselves overprinted by M21 grandite-rich layers the development of coronal garnet does not reflect a continuous P-T-t path. Rather, it more probably reflects the partial re-equilibration of M21 contact metamorphic assemblages to post-M22 conditions.  相似文献   

9.
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   

10.
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   

11.
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   

12.
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   

13.
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   

14.
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   

15.
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   

16.
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   

17.
 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   

18.
Eclogite facies carbonate rocks have been discovered associated with the granulite–eclogite transitional rocks within Bergen Arc system, Caledonian Orogen of western Norway. The local occurrences of marbles and calc‐silicates are found subparallel to the mafic eclogite facies shear zones on Holsnøy Island. Marbles contain the assemblage calcite (Ca0.99Sr0.01CO3), calcian strontianite (Ca0.18?0.44Sr0.53?0.84CO3), clinopyroxene (Jd7?32), epidote/allanite (Ps0?33), titanite, garnet (Alm52?56Grs28?33Pyp11?16), barite (Ba0.90?0.99Sr0.01?0.10SO4), celestine (Sr0.67?0.98Ba0.01?0.23Ca0.01?0.11SO4), and one apparently homogeneous grain of intermediate composition (Ba0.49Ca0.01Sr0.50SO4). Adjacent eclogites have clinopyroxene with similar jadeite contents (Jd14?34) and similar garnet (Alm51?60Grs26?36Pyp8?14) compositions. The marbles have high contents of Sr (9500–11000 p.p.m) and Y (115–130 p.p.m). However, low concentrations of some key trace elements (110–160 p.p.m. Ba and <5 p.p.m. Nb) appear to indicate that the marble is not a metamorphosed carbonatite. The 87Sr/86Sr ratios range from 0.7051 to 0.7059. Field and petrological relationships suggest that metasomatic reactions and fluids played a significant role in producing and/or modifying the marbles. The breakdown of scapolite in the granulite into carbonates and sulphates during eclogite facies metamorphism may have contributed to the metasomatic formation of the marbles along shear zones. Fluids involved during subduction are an important catalyst for metamorphism and are recognized to have played a critical role in the localized transformation from granulite to eclogite in the Holsnøy Island area. Thermobarometry indicates 640–690 °C and 18–20 kbar for adjacent eclogites and temperatures of 580–650 °C for the calc‐silicates. The marble assemblages are consistent with fluid that is dominantly comprised of H2O (XCO2 < 0.03) under high‐pressure conditions. Phase equilibria of the marbles constrain the fO2 of the fluids and imply oxidizing conditions of the deep crustal fluids. At present the source of the fluids remains unresolved. The results provide additional insights into the variable and evolving nature of fluids related to subduction and high‐pressure metamorphism.  相似文献   

19.
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   

20.
Meteoric sphaerosiderite lines (MSLs), defined by invariant δ18O and variable δ13C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre‐scale FeCO3 nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well‐preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO3) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca2+, Mg2+ and Mn2+ for Fe2+. Examples of diagenetically altered Cretaceous sphaerosiderite‐bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic δ18O and δ13C values are preserved. All three units contain poikilotopic calcite cements with significantly different δ18O and δ13C values from the co‐occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant δ18O vs. δ13C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric δ18O and δ13C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end‐member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water.  相似文献   

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