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.     

Reaction textures in scapolite–wollastonite–grossular calc-silicate rock from the Kerala Khondalite Belt, Southern India: evidence for high-temperature metamorphism and initial cooling

Scapolite–wollastonite–grossular bearing calc-silicate rocks from the Vellanad area in the Kerala Khondalite Belt (KKB) of Southern India preserve a number of reaction textures which help to deduce their P–T–fluid history. Textures include calcite+plagioclase±quartz symplectites after scapolite, grossular+quartz coronas between wollastonite and plagioclase, grossular coronas between wollastonite and plagioclase+calcite that replace former scapolite, and grossular blebs replacing anorthite+calcite+quartz pseudomorphs of scapolite. Garnet coronas are also observed between clinopyroxene and wollastonite or scapolite or plagioclase. The reactions, apart from those involving clinopyroxene, can be modelled in the simple CaO–Al₂O₃–SiO₂–CO₂ system and interpreted using partial reaction grids constructed for the activities of end-members in the analysed phases. The reaction topologies produced are good approximations for the peak as well as retrograde mineral assemblages and reaction textures. For the compositions of the phases present in this study, the medium pressure calc-silicate assemblages are defined by the stable pseudo-invariant points [Qtz], [Mei] and [Grs]. The textural features interpreted using these activity-corrected grids indicate a phase of isobaric cooling from about 835°C to 750°C at 6 kbar in the Vellanad area. This is inconsistent with earlier studies on other lithologies from the KKB, most of which imply a post-peak P–T path involving near-isothermal decompression. However, as the temperatures obtained for the KKB from the calc-silicates are higher than those previously deduced from metapelites and garnet–orthopyroxene assemblages, the phase of near-isobaric cooling reported here is inferred to have proceeded prior to the onset of the decompression documented from studies of other rock types.     

Fluid-rock history of granulite facies humite-marbles from Ambasamudram, southern India.

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 X_CO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest X_CO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at X_CO2 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 X_CO2 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 X_H2O.     

http://www.sciencedirect.com/science/article/pii/S1674987112000655

Four different varieties of charnockitic rocks,with different modes of formation,from the Mesoproterozoic Natal belt are described and new C isotope data presented.Excellent coastal exposures in a number of quarries and river sections make this part of the Natal belt a good location for observing charnockitic field relationships.Whereas there has been much debate on genesis of charnockites and the use of the term charnockite.it is generally recognized that the stabilization of orthopyroxene relative to biotite in granitoid rocks is a function of low aH₂O（±high CO₂）,high temperature,and composition （especially Fe/（Fe +Mg））.From the Natal belt exposures,it is evident that syn-emplacement.magmatic crystallization of chamockite can arise from mantle-derived differentiated melts that are inherently hot and dry（as in the Oribi Gorge granites and Munster enderbite）,as well as from wet granitic melts that have been affected through interaction with dry country rock to produce localized charnockitic marginal facies in plutons（as in the Portobello Granite）.Two varieties of post-emplacement sub-solidus chamockites are also evident.These include charnockitic aureoles developed in leucocratic,biotite.garnet granite adjacent to cross-cutting enderbitic veins that are attributed to metamorphic-metasomatic processes（as in the Nicholson’s Point granite,a part of the Margate Granite Suite）,as well as nebulous,patchy charnockitic veins in the Margate Granite that are attributed to anatectic metamorphic processes under low-aH_O fluid conditions during a metamorphic event.These varieties of chamockite show that the required physical conditions of their genesis can be achieved through a number of geological processes,providing some important implications for the classification of charnockites,and for the interpretation of charnockite genesis in areas where poor exposure obscures field relationships.     

Low-density CO2-rich fluid inclusions from charnockites of southwestern Madurai Granulite Block, southern India; implications on graphite mineralization

Characterization of fluid inclusions in graphite-bearing charnockites from the southwestern part of the Madurai Granulite Block in southern India reveals a probable relation with the formation and break down of graphite during the high-grade metamorphism. The first-generation monophase pure CO₂ inclusions, the composition of which is confirmed by laser Raman spectroscopy, recorded moderate density (0.77–0.87 g/cc) corresponding to low tapping pressure (around 2 kb) than that of the peak granulite-facies metamorphism. The precipitation of graphite, as inferred from graphite inclusions and δ¹³C values of the graphite from the outcrops, is interpreted as the cause of this lowering of fluid density. An intermediate generation of pseudosecondary inclusions resulted from the re-equilibration or modification of the first-generation fluids and the CO₂ formed is interpreted to be the oxidation product from graphite. The youngest generation of fluids which caused widespread retrogression of the granulites is a low-temperature (350 °C) high-saline (32.4–52.0 wt% NaCl equivalent) brine. Carbon isotope data on the graphite from the charnockites show δ¹³C values ranging from −11.3 to −19.9‰, suggesting a possibility of mixing of carbon sources, relating to earlier biogenic and later CO₂ fluid influx. Combining the information gathered from petrologic, fluid inclusion and carbon stable isotope data, we model the fluid evolution in the massive charnockites of the southwestern Madurai Granulite Block.     

Ultrahigh-Temperature Metamorphism in Madurai Granulites, Southern India: Evidence from Carbon Isotope Thermometry

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.     

Carbon isotope anatomy of a single graphite crystal in a metapelitic migmatite revealed by high-spatial resolution SIMS analysis

High-spatial resolution carbon isotope analyses of natural graphite using secondary ion mass spectrometry (SIMS), together with conventional mass spectrometry techniques, demonstrate isotopic heterogeneity within single graphite crystals precipitated from a partially melted metamorphic rock. SIMS ¹³C/¹²C measurements were calibrated using an internal graphite standard previously analyzed by conventional isotope ratio mass spectrometry, which gave a reproducibility of 0.3‰ (1σ) at a spatial resolution of 2–3 μm. This resolution helped to identify an unusual carbon isotope distribution in a single graphite crystal from a metapelitic leucosome, showing remarkable core to rim variations with sharp δ¹³C steps up to 10‰. The results suggest that the graphite crystal grew from one edge to other forming layers perpendicular to the c-axis. The sharp isotopic steps indicate the presence of disequilibrium carbon isotope zoning in graphite and points to the possible existence of carbon isotope sector zoning. Intra-crystalline carbon isotope disequilibrium in graphite is believed to have resulted from the difference in diffusivity between ¹²C and ¹³C in the growth medium to the interface of graphite precipitation in different growth sectors.