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1.
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   

2.
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   

3.
The temperature dependence of carbon isotopic fractionations between calcite and graphite, and between dolomite and graphite are calibrated by the calcite-dolomite solvus geothermometry using marbles collected from the contact metamorphic aureole in the Kasuga area, central Japan. The carbon isotopic fractionations (Δ13CCc-Gr and Δ13CDoGr) systematically decrease with increasing metamorphic temperature. The concordant relationships between the fractionations and solvus temperatures are approximately linear with T?2 over the temperature range. 400° to 680°C: Δ13CCcGr (%.) = 5.6 × 106 × T?2 (K) ? 2.4 Δ13CDoGr (%.) = 5.9 × 106 × T?2 (K) ? 1.9 These systematic relationships between fractionation and temperature suggest that carbon isotopic equilibria between carbonates and graphite were attained in many cases. The equation for the calcite-graphite system has a slope steeper than Bottinga's (1969) results. It is, however, in good agreement with that of Valley and O'Neil (1981) in the temperature range from 600° to 800°C.Because of the relatively high sensitivity to temperature, these isotopic geothermometers are useful for determining the temperatures in moderate- to high-grade metamorphosed carbonate rocks.  相似文献   

4.
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   

5.
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   

6.
In-situ ion microprobe measurements of carbon isotopic compositions of graphite were made in seven metasediments and two carbonate rocks from the ca. 3.8 Ga Isua supracrustal belt, West Greenland. The δ13C values of micron-scale graphite globules in the metasediments and the carbonate rocks vary from -18 to +2‰ and from -7 to -3‰, respectively. The maximum δ13C value of graphite globules in the metasediment rises from -14 to -5‰, as the metamorphic grade increases from epidote-amphibolite to upper amphibolite facies. In a single hand specimen, the δ13C values of graphite inclusions in garnet are ∼7‰ lower on average than those outside garnet. Similarly, graphite armored by quartz apparently shows a few permil lower δ13C values than those on grain boundaries between noncarbonate minerals. The fact that early crystallized minerals include relatively 13C-depleted graphite indicates that the regional metamorphism increased the δ13C values of the Isua graphite. This is consistent with the regional trend of 13C-enrichment accompanied by the increase of metamorphic grade. The minimum fractionation between graphite and carbonate is consistent with the equilibrium fractionation at about 400 to 550 °C. These observations indicate that isotopic exchange with isotopically heavy carbonate caused 13C-enrichment of Isua graphite. The δ13C values of graphite reported here (δ13C > -18‰) were produced either as a metamorphic modification of organic carbon with initially much lower δ13C values, or as an abiological reaction such as decomposition of carbonate. If the isotopic exchange between carbonate and graphite during regional metamorphism controlled the 13C-enrichment of Isua graphite, previously reported large 13C-depletion of graphite, especially armored by apatite (Mojzsis et al., 1996) was probably premetamorphic in origin. This supports the existence of life at Isua time (ca. 3.8 Ga).  相似文献   

7.
《International Geology Review》2012,54(15):1864-1875
ABSTRACT

In the mines of the Nacional de Grafite Company around Itapecerica (Minas Gerais), located in the southern Sao Francisco Craton, occurs a supracrustal succession of high-grade metamorphic rocks including quartzite, garnet-biotite gneiss, and graphite schist formed in the Palaeoproterozoic (2.0 Ga). During metamorphic processes, organic matter was progressively transformed into graphite. From four graphite samples of three different mines (two samples from high-grade metamorphic graphite schist and two generated by hydrothermal recrystallization of the graphite schist), the origin and formation temperature of this mineral was obtained by C isotopes, X-ray diffraction (XRD), and Raman spectroscopy. The values of δ13C range between ?21.23 and ?27.89 ‰, indicating that the source of the graphite was a primitive biogenic carbon material. High-grade metamorphic graphites show average temperatures around 729°C, while hydrothermal recrystallizated graphites (vein-graphites) show temperatures around 611°C by XRD, which correspond to granulite- to amphibolite facies conditions. The hydrothermal process with percolation of C-O-H fluids leads to a decrease in the crystal size along stacking direction (Lc(002)) when compared with the previously formed high-grade metamorphism graphites. An update of the current tectonic model about the collisional process during Rhyacian-Orosirian orogeny in the Sao Francisco Craton is proposed to insert the formation of the Itapecerica graphite-rich metasedimentary sequence.  相似文献   

8.
Abstract ‘Peak’metamorphic carbon isotope fractionations between calcite and graphite (ΔCal–Gr) in marbles and calc-silicates from the Cucamonga granulite terrane (San Gabriel Mountains, California) range from 3.48 to 2.90%. The data are used to test three previously published calibrations of the calcite–graphite carbon isotope thermometer. An empirical calibration of the calcite–graphite carbon isotope thermometer gives temperatures of 700–750°C; a theoretical–experimental calibration of the system gives temperatures of 760°–870°C; an experimental calibration gives temperatures of 870–1300°C. Temperatures calculated using the empirical calibration are in agreement with those calculated from garnet-based cation exchange thermometry when uncertainty is considered. Temperatures calculated using the theoretical–experimental calibration overlap the upper range of cation exchange thermometry temperatures and range to 50°C higher. The experimental calibration yields temperatures from 50 to 480°C higher than those from cation exchange thermometry. Moreover, temperatures from the experimental calibration are also inconsistent with mineral and melt equilibria in the granulite phase assemblage. Despite the better agreement between cation exchange thermometry and the empirical calibration of the calcite–graphite system, temperatures calculated using the theoretical–experimental calibration may be real peak metamorphic temperatures. If retrograde diffusion partially reset garnet-based cation exchange thermometers by c. 50°C, then the cation exchange temperatures are consistent with those from the theoretical–empirical calibration. Thermometric evidence from biotite dehydration melting equilibria is consistent with either the empirical calibration if melting was fluid-present, or the theoretical–experimental calibration if melting was fluid-absent.  相似文献   

9.
Graphite bearing marbles occur in the regional metamorphic complex of Naxos over a continuous temperature range of 380 to 670°C. The graphite is of biogenic origin and changed its original isotopic composition towards values in equilibrium with the calcite. Partial isotope exchange took place at temperatures as low as 380°C, but near equilibrium values were generally not reached below 550°C. The data agree better with the theoretically derived fractionation curve of Bottinga (1969) than with the empirical curve proposed by Valley and O'Neil (1981). We believe that the system will not provide a good thermometer.  相似文献   

10.
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   

11.
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   

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.
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   

14.
Quartz–garnet oxygen isotope thermometry of quartz‐rich metasedimentary rocks from the southern Adirondack Highlands (Grenville Province, New York) yields metamorphic temperatures of 700–800 °C, consistent with granulite facies mineral assemblages. Samples from the Irving Pond quartzite record Δ18O(Qtz–Grt) = 2.68 ± 0.21‰ (1 s.d. , n = 15), corresponding to peak metamorphic conditions of 734 ± 38 °C. This agrees well with the estimates from garnet–biotite exchange thermometry. Similar temperature estimates are obtained from Swede Pond (682 ± 47 °C, n = 3) and King's Station (c. 700 °C). The Whitehall area records higher temperatures (798 ± 25 °C, n = 3). All of these temperatures are higher than previous regional temperature estimates. The c. 800 °C temperatures near Whitehall are consistent with preservation of pre‐granulite contact temperatures adjacent to anorthosite. The preservation of peak metamorphic temperatures in garnet of all sizes is consistent with slow oxygen diffusion in garnet, and closure temperatures of at least 730 °C. Peak metamorphic fractionations are preserved in rocks with varying quartz:feldspar ratios, indicating that the modal percentage of feldspar does not affect retrograde oxygen exchange in these rocks. The lack of this correlation suggests slow rates of oxygen diffusion in quartz and feldspar, consistent with the results of anhydrous oxygen diffusion experiments.  相似文献   

15.
Fractionations of carbon and oxygen isotopes and magnesium between coexisting dolomite and calcite have been determined for marbles and calcareous schists of a wide variety of metamorphic environments from Vermont and the Grenville Province of Ontario. Concordant equilibrium fractionations are given by 83% of the samples. Calibration of the isotopic thermometers using the Mg-calcite solvus thermometer gave in the temperature range: 650°>T°>100°C $$ \begin{gathered} 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.45 (10^6 T^{ - 2} ) - 0.40 \hfill \\ 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.18 (10^6 T^{ - 2} ) + 0.17. \hfill \\ \end{gathered} $$ These isotopic fractionation expressions differ significantly from the experimentally derived relations, including the dolomite-Mg-calcite C13 partial exchange experiments of this study. Temperature ranges obtained for the metamorphic zones of Vermont are: chlorite zone, 210° to 295° C; biotite zone, 255° to 400° C; staurolite-kyanite zone, 110° to 550° C. In amphibolite-facies rocks the quenched partition relations can be complex. The temperature of quench or recrystallization may be as large as 400° C below the inferred metamorphic maximum. Oxygen isotope disequilibrium in high grade rocks, particularly from the Chester dome area, Vermont, is characterized by large negative δO D 18 –δO Ct 18 values. The size of the equilibrium exchange system for carbon and oxygen isotopes and magnesium is small, less than a few inches across the inferred relict bedding. This is attributed to the lack of a mobile pore fluid except in systems undergoing decarbonation. C13/C12 ratios in Grenville and Vermont marbles and O18/O16 ratios in Grenville and greenschist-facies Vermont carbonates span the range of ancient limestones. Staurolite-kyanite zone calcareous schists and marbles from the Chester dome area, Vermont are depleted in O18(δO18=12 to 20‰) due to equilibrium or disequilibrium decarbonation and some partial exchange. Extrapolation of the dolomite-calcite fractionation expressions to 20° C indicates that dolomite is enriched in O18 by about 4.9‰ and in C13 by about 2.4‰.  相似文献   

16.
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   

17.
Carbon isotope fractionation between coexisting calcite and grpahite ( 13Ccc-gr) has been determined in metamorphosed limestones and calc-silicate rocks from the Ryoke metamorphic belt in the northern Kiso district. In this district, the Ryoke metamorphic rocks, ranging from the lower greenschist facies to the upper amphibolite facies, are widely distributed. The fractionation of 13C/12C between calcite and graphite decreases regularly with increasing metamorphic grade and is independent of absolute 13C values of calcite. This evidence suggests that carbon isotopic exchange equilibrium has been attained during metamorphism even in the greenschist facies and isotopic modification, possibly caused by retrogressive metamorphism, is not distinguished. For T=270–650° C, the fractionation is expressed by the following equation: 13Ccc-gr=8.9×106T–2–7.1 (T in °K).This equation has a slope steeper than the current results on the 13Ccc-gr versus 106T–2 diagram. It can be used as a potential geothermometer for almost the entire temperature range of metamorphism. 13C values of carbonaceous matter in unmetamorphosed limestones in this district are approximately –22, due to its biogenic origin. Graphite from metamorphosed limestones is also considered to be of biogenic origin but shows enrichment of 13C due to isotopic exchange with calcite. 13C values of graphite as well as 13Ccc-gr confirm that zone II represents the lowest grade zone of Ryoke metamorphism. The maximum equilibrium fractionation of 13C between calcite and graphite is considered to be approximately 23%, which corresponds to 270° C. Below this temperature, it seems that carbon isotopic exchange between the minerals does not occur.Calcite in marble from the higher grade zones has relatively lower 13C and 18O values. The depletion of heavy isotopes is considered to be caused by the loss of 13C and 18O enriched carbon dioxide during decarbonation reactions. For oxygen, it is considered that isotopic exchange with metamorphic fluids plays an important role in lowering the 18O value of calcite in some higher grade marbles.  相似文献   

18.
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   

19.
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   

20.
Calcite–dolomite solvus geothermometry is a versatile method for the estimation of metamorphic temperature because of its simplicity. However, in medium‐ to high‐grade metamorphic rocks the accuracy of estimating temperature by the integration of unmixed dolomite and calcite is hampered by the heterogeneous distribution of unmixed dolomite, difficulties in distinguishing between preexisting and exsolved dolomite and demarcating grain boundaries. In this study, it is shown that calcite–dolomite solvus thermometry can be applied to calcite inclusions in forsterite and spinel for the estimation of peak metamorphic temperature in granulite facies marbles from Skallevikshalsen, East Antarctica. The marbles are comprised of a granoblastic mineral assemblage of calcite + dolomite + forsterite + diopside + spinel + phlogopite ± apatite, characteristic of granulite facies metamorphic conditions. Forsterite, spinel and apatite frequently contain ‘negative crystal’ inclusions of carbonates that display homogeneously distributed dolomite lamellae. On the basis of narrow ranges of temperature (850–870 °C) recorded from carbonate inclusions compared with the range from matrix carbonate it is regarded that the inclusion carbonates represent a closed system. Furthermore, this estimate is consistent with dolomite–graphite carbon isotope geothermometry, and is considered to be the best estimate of peak metamorphic temperature for this region. Matrix calcite records different stages of retrograde metamorphism and re‐equilibration of calcite that continued until Mg diffusion ceased at 460 °C. Electron backscattered diffraction (EBSD) results together with morphological features of unmixed coarse tabular dolomite suggest anisotropic diffusion and mineral growth are influenced by crystallographic orientation. Identification of sub‐grain boundaries and formation of fine‐grained unmixing in calcite rims suggest the presence of grain boundary fluids in the late retrograde stages of metamorphic evolution. These results, thus, demonstrate the usefulness of carbonate inclusion geothermometry in estimating the peak metamorphic temperatures of high‐grade terranes and the application of EBSD in understanding the unmixing behaviour of minerals with solid solutions.  相似文献   

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