Empirical tests of carbon isotope thermometry in granulites from southern California

Abstract ‘Peak’metamorphic carbon isotope fractionations between calcite and graphite (Δ_Cal–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.     

Calcite–graphite isotope thermometry in amphibolite facies marble, Bancroft, Ontario

This study presents calcite–graphite carbon isotope fractionations for 32 samples from marble in the northern Elzevir terrane of the Central Metasedimentary Belt, Grenville Province, southern Ontario, Canada. These results are compared with temperatures calculated by calcite–dolomite thermometry (15 samples), garnet–biotite thermometry (four samples) and garnet–hornblende thermometry (three samples). Δ_cal‐gr values vary regularly across the area from >6.5‰ in the south to 4.0‰ in the north, which corresponds to temperatures of 525 °C in the south to 650 °C in the north. Previous empirical calibration of the calcite–graphite thermometer agrees very well with calcite–dolomite, garnet–biotite and garnet–hornblende thermometry, whereas, theoretical calibrations compare less well with the independent thermometry. Isograds in marble based on the reactions rutile + calcite + quartz =titanite and tremolite + calcite + quartz = diopside, span temperatures of 525–600 °C and are consistent with calculated temperature–X(CO₂) relations. Results of this study compare favourably with large‐scale regional isotherms, however, local variation is greater than that revealed by large‐scale sampling strategies. It remains unclear whether the temperature–Δ_cal‐gr relationship observed in natural materials below 650 °C represents equilibrium fractionations or not, but the regularity and consistency apparent in this study demonstrate its utility for thermometry in amphibolite facies marble.     

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).     

Graphite content and isotopic fractionation between calcite-graphite pairs in metasediments from the Mgama Hills,Southern Kenya

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.     

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.     

Carbon isotopic thermometry calibrated by dolomite-calcite solvus temperatures

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 (Δ¹³C_Cc-Gr and Δ¹³C_DoGr) 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: Δ¹³C_CcGr (%.) = 5.6 × 10⁶ × T^?2 (K) ? 2.4 Δ¹³C_DoGr (%.) = 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.     

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.     

Carbon isotope exchange during polymetamorphism in the Panamint Mountains, California, USA

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.     

Oxygen isotope composition of carbonates,silicates, and oxides in selected carbonatites: constraints on crystallization temperatures of carbonatite magmas

Oxygen isotope compositions and fractionations between calcite (Cc) and magnetite (Mt), diopside-rich clinopyroxene (Di), monticellite (Mnt), kimzeyite-rich garnet (Gt), and biotite (Bt) were measured for carbonatites from Oka (Canada), Magnet Cove (USA), Jacupiranga (Brazil), and Essonville (Canada), to obtain crystallization temperatures and explore the crystallization history of carbonatites. The highest isotopic temperatures are obtained from Cc–Mt fractionations from Oka (745–770 °C) and Cc–Mnt fractionations from Magnet Cove (700 and 760 °C). Cc–Mt temperatures for very coarse-grained, euhedral magnetite phenocrysts and calcite from Jacupiranga are 700 °C. In samples that contain diopside and magnetite, the Cc–Mt temperatures are always higher than Cc–Di temperatures. This difference is consistent with crystallization of magnetite before diopside, minor retrograde resetting of magnetite isotopic compositions, and the order of crystallization inferred from inclusions of Mt in Di. Cc–Mt, Cc–Di, and Cc–Mnt fractionations are thus interpreted to represent those established during crystallization at rapid cooling rates (10³–10⁴ °C/my). Diffusion model calculations indicate that at slower post-crystallization cooling rates (10–10² °C/my), magnetite compositions should experience significant isotopic resetting by diffusional exchange with Cc, Bt, and apatite, and yield lower temperatures than Cc–Di. Cc–Bt fractionations correspond to the lowest temperatures (440–560 °C). Although some of these are relatively high isotopic temperatures for biotite, they most likely represent those established during subsolidus retrograde exchange between biotite and calcite during rapid subsolidus cooling.     

Hornblende geothermometry of amphibolite layers of the Popple Hill gneiss, north-west Adirondack Lowlands, New York, USA

The exchange reaction tschermakite+2 diopside+2 quartz=tremolite+2 anorthite (HPCQ), in combination with the thermodynamic database TWQ (version 1.02, Berman, 1991), has been evaluated for its usefulness as a geothermometer. This reaction, which is both water conserving (independent of water fugacity) and which does not require the presence of garnet, is well suited for studying pyroxene‐bearing amphibolites. As an application of this geothermometer, we have re‐examined the amphibolites occurring in the Popple Hill gneiss of the Adirondack Lowlands of New York, USA, to better understand the magnitude of temperature variation preserved in the amphibolites themselves in this classic locality. At an assumed constant pressure of 7 kbar, the temperatures range from 619 to 682 °C from Edwards to Pierrepont and are uncorrelated with either distance along the strike of the region or with modal mineralogical variations. Hornblende exhibits a narrow compositional range suggesting that there has been little or no thermal gradient along the strike of the Lowlands. Temperatures recorded just north of Colton are, however, distinctly higher (694–758 °C). Although it is likely that the Popple Hill gneiss amphibolites experienced some effects of progressive metamorphism, particularly in the vicinity of Colton, the variations in modal mineralogy are most likely the result of such factors as local variations in the bulk chemistry of the protolith and in the fugacity of H₂O due to infiltration of diluting species (e.g. CO₂, CH₄), rather than a regional temperature variation. Temperatures recorded by the HPCQ geothermometer reported here are similar in magnitude and geographic trend to those reported for graphite–calcite carbon‐isotope thermometry by Kitchen & Valley (1995), suggesting that peak metamorphism in the Adirondack Lowlands involved laterally extensive and fairly uniform isotherms.     

Calibration of oxygen isotope fractionation and calcite-corundum thermometry in emery at Naxos,Greece

Corundum (Crn), including sapphire, occurs in emery pods surrounded by marble on the island of Naxos, Greece. The emery formed from bauxite deposited in karst that was metamorphosed to 400–700°C at 20–15 Ma. Many of these rocks initially appeared well suited for refractory accessory mineral (RAM) thermometry, which uses oxygen isotope fractionation between a RAM – corundum – and a modally dominant phase with faster diffusion of oxygen – calcite (Cc) – to determine peak metamorphic temperatures. However, previous attempts at oxygen isotope thermometry were confounded by highly variable fractionations (Δ¹⁸O) measured at mm-scale and the uncertain calibration of Δ¹⁸O(Cc-Crn) versus temperature. Secondary ion mass spectrometry (SIMS) permits in situ analysis of δ¹⁸O in corundum and calcite at the 10-μm scale in adjacent grains where textures suggest peak metamorphic equilibrium was attained. SIMS analyses of adjacent mineral pairs in eight rocks yield values of Δ(Cc-Crn) that systematically decrease from 7.2 to 2.9‰ at higher metamorphic grade. Pairing these data with independent temperature estimates from mineral isograds yields an empirical calibration of 1,000 lnα(Cc-Crn) = 2.72 ± 0.3 × 10⁶/T² (T in K). The new fractionations (2.7‰ at 1,000 K) are significantly smaller than those calculated from the modified increment method (6.5‰ at 1,000 K; Zheng, Geochimica et Cosmochimica Acta, 1991, 55:2299–2307; Zheng, Mineral Mag, 1994, 58A:1000–1001), which yield unreasonably high temperatures of 630 to 1,140°C when applied to the new Naxos data. The new calibration of Δ(Cc-Crn) can be combined with published fractionations to calculate A-factors for corundum versus a range of 14 other minerals. These new fractionation factors can be used for thermometry or to constrain the genesis of corundum. A compilation of gem corundum δ¹⁸O values shows that many igneous sapphires, including important deposits of basalt-associated sapphire, are mildly elevated in δ¹⁸O relative to the calculated range in equilibrium with mantle values (4.4–5.7‰) and formed from evolved magmas.     

13C12C exchange between calcite and graphite: A possible thermometer in Grenville marbles

The fractionation of ¹³C between calcite and graphite, Δ(Cc-Gr). is consistently small (2.6–4.8 permil) in 34 assemblages from upper amphibolite- and granulite-facies marbles of the Grenville Province. In 25 samples from the Adirondack Mountains, New York, it decreases regularly with increasing metamorphic temperature. The fractionations are independent of absolute δ¹³C values of calcite (?2.9 to +5.0). For T = 600–800°C, the Adirondack data are described by Δ(Cc-Gr) = ?0.00748T (°C) + 8.68. This good correlation between Δ and T suggests that carbon isotope equilibrium was attained in these high-grade marbles and that the theoretical calculations of this fractionation by Bottinga are approximately 2 permil too large in this temperature range. Because of the relatively high temperature sensitivity suggested by these results and by Bottinga's calculations, and the pressure independence of isotope fractionation, Δ(Cc-Gr) may provide a very good thermometer for high-grade marbles.Comparison of this field calibration for Δ(Cc-Gr) vs temperature with results from other terranes supports the utility of Δ(Cc-Gr) for geothermometry and suggests that graphite is much more sluggish to exchange than calcite, that exchange between calcite and graphite occurs at temperatures as low as 300°C, and that equilibrium may normally be attained only when peak metamorphic temperatures are greater than 500–600°C.Because ¹³C exchange is an unavoidable metamorphic process at temperatures above 300°C, high values of δ¹³C(Gr) in moderate- to high-grade carbonate-bearing rocks do not provide a sufficient criterion to infer an abiogenic origin for the graphite.     

The nature of gold-bearing fluids in Atud gold deposit,Central Eastern Desert,Egypt

Electron microprobe analyses of gold and associated ore minerals as well as stable isotope analyses of sulphide and carbonate minerals were performed in order to determine the metal and fluid sources and temperature of the mineralizing systems to better understand the genesis of the Atud gold deposit hosted in the metagabbro–diorite complex of Gabal Atud (Central Eastern Desert, Egypt). The gold can be classified as electrum (63.6–74.3 wt.% Au and 24.6–26.6 wt.% Ag) and is associated with arsenopyrite and As-bearing pyrite in the main mineralization (gold-sulphides) phase within the main mineralized quartz veins and altered host rocks. Based on the arsenopyrite geothermometer, As-contents (29.3–32.7 atom%) in arsenopyrite point to deposition in the Log ?_S2 and T ranges of ?10.5 to ?5.5 and 305–450°C, respectively, during the main mineralizing phase. Based on the δ³⁴S isotopic compositions of the sulphides, they are originated from magmatic fluids in which the sulphur is either sourced directly from magma or remobilized from the magmatic rocks (gabbroic rocks). On the other hand, calcite formed from fluids having mainly magmatic mixed with variable metamorphic signatures based on its δ¹³C and δ¹⁸O values. This work concluded that the gold-bearing ores at Atud deposit have magmatic sources leaching from the country intrusive rocks during water/rock interactions then remobilized during a metamorphic event. Therefore, the Atud gold deposit is classified as an intrusion-related gold deposit, in which the gabbro–diorite host intrusion acted as the source of metals which were mobilized and deposited as a result of the effects of NW–SE shearing.     

'Forbidden zone' subduction of sediments to 150 km depth— the reaction of dolomite to magnesite + aragonite in the UHPM metapelites from western Tianshan, China

The solid‐state reaction magnesite (MgCO₃) + calcite (aragonite) (CaCO₃) = dolomite (CaMg(CO₃)₂) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km^?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO₂ to the overlying mantle wedge.     

Metamorphic evolution of diamond-bearing and associated rocks from the Kokchetav Massif, northern Kazakhstan

Representative diamond-bearing gneisses and dolomitic marble, eclogite and Ti-clinohumite-bearing garnet peridotite from Unit I at Kumdy Kol and whiteschist from Unit II at Kulet, eastern Kokchetav Massif, northern Kazakhstan, were studied. Diamond-bearing gneisses contain variable assemblages, including Grt+Bt+Qtz±Pl±Kfs±Zo±Chl±Tur±Cal and minor Ap, Rt and Zrn; abundant inclusions of diamond, graphite+chlorite (or calcite), phengite, clinopyroxene, K-feldspar, biotite, rutile, titanite, calcite and zircon occur in garnet. Diamond-bearing dolomitic marbles consist of Dol+Di±Grt+Phl; inclusions of diamond, dolomite±graphite, biotite, and clinopyroxene were identified in garnet. Whiteschists carry the assemblage Ky+Tlc+Grt+Rt; garnet shows compositional zoning, and contains abundant inclusions of talc, kyanite and rutile with minor phlogopite, chlorite, margarite and zoisite. Inclusions and zoning patterns of garnet delineate the prograde P–T path. Inclusions of quartz pseudomorphs after coesite were identified in garnet from both eclogite and gneiss. Other ultrahigh-pressure (UHP) indicators include Na-bearing garnet (up to 0.14 wt% Na₂O) with omphacitic Cpx in eclogite, occurrence of high-K diopside (up to 1.56 wt% K₂O) and phlogopite in diamond-bearing dolomitic marble, and Cr-bearing kyanite in whiteschist. These UHP rocks exhibit at least three stages of metamorphic recrystallization. The Fe-Mg partitioning between clinopyroxene and garnet yields a peak temperature of 800–1000 °C at P >40 kbar for diamond-bearing rocks, and about 740–780 °C at >28–35 kbar for eclogite, whiteschist and Ti-bearing garnet peridotite. The formation of symplectitic plagioclase+amphibole after clinopyroxene, and replacement of garnet by biotite, amphibole, or plagioclase mark retrograde amphibolite facies recrystallization at 650–680 °C and pressure less than about 10 kbar. The exsolution of calcite from dolomite, and development of matrix chlorite and actinolite imply an even lower grade greenschist facies overprint at c. 420 °C and 2–3 kbar. A clockwise P–T path suggests that supracrustal sediments together with basaltic and ultramafic lenses apparently were subjected to UHP subduction-zone metamorphism within the diamond stability field. Tectonic mixing may have occurred prior to UHP metamorphism at mantle depths. During subsequent exhumation and juxtaposition of many other tectonic units, intense deformation chaotically mixed and mylonitized these lithotectonic assemblages.     

Carbon isotopic study on coexisting calcite and graphite in the Ryoke metamorphic rocks,northern Kiso district,central Japan

Carbon isotope fractionation between coexisting calcite and grpahite ( ¹³C_cc-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: ¹³C_cc-gr=8.9×10⁶T^–2–7.1 (T in °K).This equation has a slope steeper than the current results on the ¹³C_cc-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 ¹³C_cc-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.     

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.     

Apparent oxygen isotope equilibrium during progressive foliation development and porphyroblast growth in metapelites: implications for stable isotope and conventional thermometry

The assumption of oxygen isotope and major element equilibrium during prograde metamorphism was tested using staurolite‐grade pelitic schists that have undergone sequential porphyroblast growth and multiple episodes of recrystallization of matrix minerals and foliation development. Textural relationships are used to infer a metamorphic history that involves garnet growth followed by staurolite growth, with each porphyroblast growth event followed by at least one period of recrystallization of matrix minerals. Conventional geothermobarometry using Qtz–Grt–Pl–Ms–Bt ± St equilibria yields peak P–T conditions of c. 625 °C at 9–11 kbar, consistent with KMnFMASH petrogenetic grid predictions for stability of the assemblage Grt + St + Bt. Qtz–Grt oxygen isotope fractionations yield apparent temperatures of c. 590 °C and Qtz–St fractionations yield an apparent temperature of c. 595 °C. Diffusional modelling indicates that quartz isotopic compositions were reset by c. 30 °C via retrograde isotopic diffusional exchange with micas. The isotopic temperatures appear to be in excellent agreement with one another, and suggest oxygen isotope equilibrium was attained between garnet and staurolite at c. 625 °C. However, the agreement of Qtz–Grt and Qtz–Str isotopic temperatures is not consistent with petrographic observations (garnet grew before staurolite) and petrogenetic grid constraints that predict that garnet grows over a temperature interval of c. 525–550 °C. Given that: (i) oxygen diffusion rates in staurolite and garnet are slow enough to render an individual porphyroblast effectively closed to exchange after it forms; and (ii) matrix minerals are able to exchange isotopes via recrystallization during each period of deformation; garnet and staurolite could not have simultaneously achieved oxygen isotope equilibrium with each other or with minerals in the recrystallized matrix. Thus, the Qtz–Grt fractionations, which yield apparent temperatures that are in apparent agreement with peak metamorphic temperature and apparent temperatures for Qtz–St fractionations, cannot be fractionations resulting from equilibrium isotopic exchange. Instead, they are apparent fractionations between porphyroblasts formed at different temperature and times in the prograde P–T–D path, and quartz that recrystallized and exchanged with micas and plagioclase during several phases of deformation.     

Partitioning of strontium between calcite,dolomite and liquids: An experimental study under higher temperature diagenetic conditions,and a model for the prediction of mineral pairs for geothermometry

The partitioning of Sr between calcite, dolomite and liquids is essentially independent of temperature between 150° and 350° C. The partition coefficients corrected for number of cation sites are b _calc=0.096 and b _dol= 0.048 for 1 mol cations/6 mol H₂O liquid. Upon dilution the partition coefficients increase, but their ratio stays constant at about 2∶1. This ratio is due to the fact that calcite has twice as many Ca-sites for Sr-substitution as dolomite. The 2∶1 relationship is also observed in natural calcite and dolomite which have undergone diagenesis. The temperature independence of partitioning is caused by the relatively small thermal expansion of calcite and dolomite. Thermal expansion between 25° and 400° C was found to follow the equations V _calc=7.0·10⁻⁴ T(°C)+36.95 and V _dol=6.9·10⁻⁴ T(°C)+32.24, V: cm³/mol. Therefore calcite and dolomite cannot serve as a temperature indicator. To have an ideal geothermometer a mineral pair with high and low thermal expansion is required. Literature date demonstrate that wurtzite, sphalerite, and galena are such minerals.     

Fluid infiltration during contact metamorphism of interbedded marble and calc-silicate hornfels, Twin Lakes area, central Sierra Nevada, California

Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO₂-H₂O fluid compositions of χCO₂= 0.61–0.74 in the marbles and χCO₂= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO₂ diagrams in the model system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 10⁴ cm³/cm² and 4.8–12.9 × 10⁴ cm³/cm², respectively. For an estimated duration of metamorphism of 10⁵ years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10^?6 D in the marbles and 10–27 × 10^?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.