Constraints on the application of carbon isotope thermometry in high- to ultrahigh-temperature metamorphic terranes

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 f_O2 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.     

Fluid flow patterns and infiltration isograds in melilite marbles from the Bufa del Diente contact metamorphic aureole, north-east Mexico

In the inner aureole of the Bufa del Diente alkali syenite (north-east Mexico), thin calcareous argillite bands horizontally embedded in impure marbles acted as contact-metamorphic aquifers for hypersaline brines of magmatic origin. Thick-bedded marbles were largely impervious. From 180 m up to the intrusion contact, argillites were completely decarbonated, resulting in melilite + wollastonite + phlogopite + perovskite-bearing parageneses. In marbles, this assemblage is confined to a narrow 7-12-m-wide infiltration zone adjacent to the contact. Up to this distance, calcite + wollastonite + diopside + alkali feldspar + titanite was stable, indicating that the fluid evolution in these marbles was internally buffered. Brine infiltration from the metaargillite aquifer into the marbles occurred perpendicular to the marble-metaargillite boundaries and was confined to a zone 4-6 cm wide above the boundaries. This is documented by the three reactions Cc + Di = Mel + CO₂, (1) Cc + Kfs + Di + H₂O = Phl + Wo + CO₂, (2) Cc + Ttn = Prv + Wo + CO₂, (3) Melilites (Ak_32-45Gh_13-32Sm_32-40 to Ak_52-72Gh_0-1Sm_28-48) occur as rims around diopsides and become continuously thicker towards the metaargillite beds. Fluid inclusion observations suggest that the infiltrating brine was hypersaline (NaCl + KCl_cq～ 65 wt%) and that the reactions took place at the water-rich side of the H₂O-CO₂-salts immiscibility field at about 600d? C (2, 3) and 660 to 680d? C (1) at P～ 1200 bar and X_co2～ 0.02. Mass balance calculations show that the amount of brine infiltrated from the aquifer into the marble was very low and decreased continuously with increasing distance from the boundary. The maximum width of brine infiltration was about 6 cm. This confirms that brine flow was largely parallel to the aquifer, not perpendicular to it. The CO₂ produced by the decarbonation reactions probably escaped as an immiscible low-density H₂O-CO₂ fluid of X_co2≤ 0.5 into overlying marble via grain-edge flow. The metaargillite-marble boundary acted as a semipermeable membrane 6 cm in thickness keeping back the brine in the aquifer and losing the in-situ produced low-density CO₂-rich fluid.     

大别山苏家河地区榴辉岩和大理岩的地球化学研究

对大别山西段苏家河地区熊店和杨冲低温榴辉岩及胡家湾榴闪岩进行了详细的氢、氧和锶、钕同位素以及稀土元素和矿物化学分析。熊店榴辉岩和胡家湾榴闪岩的全岩δ＾１８Ｏ值较高（８．８‰￣１１．２‰）,而杨冲榴辉岩的全岩δ＾１８Ｏ值较低（４．３‰）,它们的全岩δＤ值为－５５‰￣７５‰。结合锶、钕同位素和稀土元素组成特征,推测苏家河榴辉岩（榴闪岩）的原岩可能为岛弧玄武岩,变质前曾与海水在不同温度下进行过氢、氧同位     

Exsolution of dolomite and application of calcite–dolomite solvus geothermometry in high‐grade marbles: an example from Skallevikshalsen,East Antarctica

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.     

13C‐rich marbles from the Proterozoic Einasleigh metamorphics,northern Queensland

Four samples of dolomitic marble from the Proterozoic Einasleigh Metamorphics of northern Queensland contain unusually high δ¹³C (5.1 to 5.9‰ PDB). A hyper‐saline depositional and diagenetic environment for these rocks adequately explains the available field and chemical evidence, and the heavy carbon signature.     

Determining the direction of contact metamorphic fluid flow: an assessment of mineralogical and stable isotope criteria

ABSTRACT One-dimensional fluid advection-dispersion models predict differences in the patterns of mineralogical and oxygen isotope resetting during up- and down-temperature metamorphic fluid flow that may, in theory, be used to determine the fluid flow direction with respect to the palaeotemperature gradient. Under equilibrium conditions, down-temperature fluid flow is predicted to produce sharp reaction fronts that separate rocks with isobarically divariant mineral assemblages. In contrast, up-temperature fluid flow may produce extensive zones of isobarically univariant mineral assemblages without sharp reaction fronts. However, during contact metamorphism, mineral reaction rates are probably relatively slow compared with fluid velocities and distended reaction fronts may also form during down-temperature fluid flow. In addition, uncertainties in the timing of fluid flow with respect to the thermal peak of metamorphism and the increase in the variance of mineral assemblages due to solid solutions introduce uncertainties in determining fluid flow directions. Equilibrium down-temperature flow of magmatic fluids in contact aureoles is also predicted to produce sharp δ¹⁸O fronts, whereas up-temperature flow of fluids derived by metamorphic devolatilization may produce gradational δ¹⁸O vs. distance profiles. However, if fluids are channelled, significant kinematic dispersion occurs, or isotopic equilibrium is not maintained, the patterns of isotopic resetting may be difficult to interpret. The one-dimensional models provide a framework in which to study fluid-rock interaction; however, when some of the complexities inherent in fluid flow systems are taken into account, they may not uniquely distinguish between up- and down-temperature fluid flow. It is probably not possible to determine the fluid flow direction using any single criterion and a range of data is required.     

Interaction of aqueous fluids with calcareous metasediments during high-T, low-P regional metamorphism in the Qadda area, southern Arabian Shield

The S.W. Nabitah Mobile Belt, Saudi Arabia, contains a Proterozoic island-arc complex. In the Qadda area, the metavolcanic-dominated supracrustal sequence records amphibolite facies regional metamorphism of high-T , low-P type. Calcsilicate rocks and aluminous dolomitic marbles within the supracrustal sequence have been studied in detail to refine estimates of peak metamorphic P–T conditions and assess the role of fluids during prograde and retrograde metamorphism. Fluid-independent thermobarometers (including the calcite–dolomite thermometer and P-sensitive equilibria involving grossular, wollastonite, anorthite, meionite, quartz and calcite) yield peak P–T conditions of c. 650–660 °C, 4 kbar, both higher than previous estimates, giving a revised average thermal gradient of c. 45 °C km^–1. The close match between the peak temperatures implied by calcite–dolomite thermometry and those recorded by univariant devolatilization equilibria suggests that the calcareous rocks were fluid-bearing during late-prograde and peak metamorphic stages. These fluids were essentially binary H₂O–CO₂ mixtures with low NaCl and HF concentrations. Most were H₂O-rich, with X_CO2 between 0.02 and 0.2, but values of c. 0.6 are recorded by two samples. High modal abundances of the solid products of decarbonation reactions (e.g. c. 10–50% wollastonite) in many of the rocks that record low-X_CO2 equilibrium fluids implies infiltration of significant quantities of externally derived aqueous fluid during late-prograde metamorphism, but not enough to exhaust the buffering capacity of the rocks. Calculated minimum time-integrated fluid-to-rock ratios of five wollastonite-bearing calcsilicate rocks range from 0.7±0.22 to 1.39±0.46 (1σ); those of six marbles range from c. 0 to 4±1.4. The latter variation occurs on a metre-scale, implying focusing of fluid flow. Diopside-rich rocks record fluid-to-rock ratios of up to 88±48. Penetrative wollastonite lineations indicate a temporal link between infiltration and distributed ductile deformation. Infiltrating fluids were probably derived both from the prograde dehydration of adjacent metabasalts and metatuffs and from crystallization of voluminous pretectonic granitoid intrusions. In general, fluid-to-rock ratios deduced for the metavolcanic-dominated Qadda area are similar to those recorded by rocks in the metasediment-dominated terrane of N. New England. The occurrence of post-tectonic retrograde hydration textures in both carbonate-bearing and carbonate-free rocks otherwise lacking hydrous minerals testifies to infiltration of aqueous fluids during retrograde metamorphism in the absence of penetrative deformation. Minimum fluid-to-rock ratios calculated for secondary grossular reaction rims in some calcsilicates are c. 0.04. Later patchy hydration of scapolite probably utilized static, pore-filling fluids remaining after the early retrograde infiltration.     

内蒙古卓资地区含磷灰石白云质大理岩的成因探讨

内蒙古卓资地区零星分布的含磷灰石白云质大理岩的成因一直是有争议的问题,争论的焦点在于它是沉积变质的碳酸盐岩还是岩浆碳酸岩。对这个问题的不同认识直接关系到这种岩石本身是否具有形成岩浆碳酸岩型磷灰石矿床的可能。本文在对含磷灰石白云质大理岩进行比较详细的地质、矿物、岩石和地球化学等诸方面研究的基础上,确认它是沉积变质的碳酸盐岩,而不是岩浆碳酸岩,该大理岩本身不具备形成岩浆碳酸岩型磷灰石矿床的条件。     

Types of carbonate aquifers according to the fracturation and the karstification in a southern Spanish area

 The analysis of the fractures in the marble forming sierras Blanca and Mijas (southern Spain), with faults of markedly different sizes and joints measured at 21 stations, demonstrate the presence of two principal directions of fractures (NNW-SSE and NNE-SSW). Other major directions of fractures, although less distinct, are N100E, N120E and N60E. The form of the karstic cavities known in these sierras was influenced by fractures, fundamentally NNW-SSE and, to a lesser extent, NNE-SSW, as well as by the mineralogical composition of the marble. All the cavities known are located in blue limestone marble and appear to have formed by the end of the Miocene, principally during the Pliocene and the Pleistocene. From a hydrogeological standpoint, Sierra Blanca and Sierra Mijas constitute a unit limited by faults oriented ENE-WSW, NNW-SSE and NNE-SSW. Specifically, fractures of the latter two directions influence the compartmentalization and the hydrogeological functioning of the unit. According to the degree of fracturing and/or karstification, three basic types (apart from intermediate situations) of aquiferous behavior have been distinguished: karstic aquifer, fissured aquifer, and porous aquifer. Received: 2 October 1995 · Accepted: 29 May 1996     

Carbon isotope thermometry in marbles of the Adirondack Mountains, New York

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 δ¹³C_cal and δ¹³C_gr. A strong correlation between carbon isotopic composition and the abundance of graphite (C_gr/C_rock) 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. C_gr/C_rock and δ¹³C_cal vs. δ¹³C_gr 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. C_gr/C_rock 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).