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.     

Contrasting fluid evolution of granulite-facies marbles: implications for a high-T intermediate-P terrain in the Famatinian Range, San-Juan, Argentina

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.     

The stable isotope signature of kilometre-scale fracturedominated metamorphic fluid pathways, Mary Kathleen, Australia

Abstract Large calcite veins and pods in the Proterozoic Corella Formation of the Mount Isa Inlier provide evidence for kilometre-scale fluid transport during amphibolite facies metamorphism. These 10- to 100-m-scale podiform veins and their surrounding alteration zones have similar oxygen and carbon isotopic ratios throughout the 200 × 10-km Mary Kathleen Fold Belt, despite the isotopic heterogeneity of the surrounding wallrocks. The fluids that formed the pods and veins were not in isotopic equilibrium with the immediately adjacent rocks. The pods have δ¹³C_calcite values of –2 to –7% and δ¹⁸O_calcite values of 10.5 to 12.5%. Away from the pods, metadolerite wallrocks have δ¹⁸O_whole-rock values of 3.5 to 7%. and unaltered banded calc-silicate and marble wallrocks have δ¹³C_calcite of –1.6 to –0.6%, and δ¹⁸O_calcite of 18 to 21%. In the alteration zones adjacent to the pods, the δ¹⁸O values of both metadolerite and calc-silicate rocks approach those of the pods. Large calcite pods hosted entirely in calc-silicates show little difference in isotopic composition from pods hosted entirely in metadolerite. Thus, 100- to 500-m-scale isotopic exchange with the surrounding metadolerites and calc-silicates does not explain the observation that the δ¹⁸O values of the pods are intermediate between these two rock types. Pods hosted in felsic metavolcanics and metasiltstones are also isotopically indistinguishable from those hosted in the dominant metadolerites and calc-silicates. These data suggest the veins are the product of infiltration of isotopically homogeneous fluids that were not derived from within the Corella Formation at the presently exposed crustal level, although some of the spread in the data may be due to a relatively small contribution from devolatilization reactions in the calc-silicates, or thermal fluctuations attending deformation and metamorphism. The overall L-shaped trend of the data on plots of δ¹³C vs. δ¹⁸O is most consistent with mixing of large volumes of externally derived fluids with small volumes of locally derived fluid produced by devolatilization of calc-silicate rocks. Localization of the vein systems in dilatant sites around metadolerite/calc-silicate boundaries indicates a strong structural control on fluid flow, and the stable isotope data suggest fluid migration must have occurred at scales greater than at least 1 km. The ultimate source for the external fluid is uncertain, but is probably fluid released from crystallizing melts derived from the lower crust or upper mantle. Intrusion of magmas below the exposed crustal level would also explain the high geothermal gradient calculated for the regional metamorphism.     

Formation of wollastonite-bearing marbles during late regional metamorphic channelled fluid flow in the Upper Calcsilicate Unit of the Reynolds Range Group,central Australia*

Abstract Granulite facies marbles from the Upper Calcsilicate Unit of the Reynolds Range, central Australia, contain metre-scale wollastonite-bearing layers formed by infiltration of water-rich (X_CO2= 0.1–0.3) fluids close to the peak of regional metamorphism at c. 700° C. Within the wollastonite marbles, zones that contain <10% wollastonite alternate on a millimetre scale with zones containing up to 66% wollastonite. Adjacent wollastonite-free marbles contain up to 11% quartz that is uniformly distributed. This suggests that, although some wollastonite formed by the reaction calcite + quartz = wollastonite + CO₂, the wollastonite-rich zones also underwent silica metasomatism. Time-integrated fluid fluxes required to cause silica metasomatism are one to two orders of magnitude higher than those required to hydrate the rocks, implying that time-integrated fluid fluxes varied markedly on a millimetre scale. Interlayered millimetre -to centimetre-thick marls within the wollastonite marbles contain calcite + quartz without wollastonite. These marls were probably not infiltrated by significant volumes of water-rich fluids, providing further evidence of local fluid channelling. Zones dominated by grandite garnet at the margins of the marl layers and marbles in the wollastonite-bearing rocks probably formed by Fe metasomatism, and may record even higher fluid fluxes. The fluid flow also reset stable isotope ratios. The wollastonite marbles have average calcite (Cc) δ¹⁸O values of 15.4 ± 1.6% that are lower than the average δ¹⁸O(Cc) value of wollastonite-free marbles (c. 17.2 ± 1.2%). δ¹³C(Cc) values for the wollastonite marbles vary from 0.4% to as low as -5.3%, and correlations between δ¹⁸O(Cc) and δ¹³C(Cc) values probably result from the combination of fluid infiltration and devolatilization. Fluids were probably derived from aluminous pegmatites, and the pattern of mineralogical and stable isotope resetting implies that fluid flow was largely parallel to strike.     

Fluid flow and mass transport at the Valentine wollastonite deposit, Adirondack Mountains, New York State

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.     

Carbon,hydrogen, and oxygen isotope studies of the regional metamorphic complex at Naxos,Greece

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 δ¹⁸O_H2O 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 δD_H2O 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 $\text{CO}{}_2\text{H}{}_2\text{O}$ 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.     

Assessment of grain-scale homogeneity and equilibration of carbon and oxygen isotope compositions of minerals in carbonate-bearing metamorphic rocks by ion microprobe

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.     

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.     

冀西北怀安杂岩的年代学、地球化学、Nd-Hf-O同位素组成及其地质意义

冀西北地区怀安杂岩由变质表壳岩和变质深成岩组成,其中变质表壳岩的形成时代、怀安杂岩的构造背景以及其与孔兹岩带间的关系一直存在较大争议.本文对怀安杂岩的几处代表性露头进行了详细野外考察,对4件样品进行了岩石学、锆石SHRIMP U-Pb定年、同位素和元素地球化学分析.所有样品都给出了1.86~1.81 Ga的变质锆石年龄,进一步支持怀安杂岩广泛遭受到古元古代晚期变质作用改造的认识.侵入/包裹含BIF表壳岩组合的变质辉长岩（HB1425）和片麻状英云闪长岩（HB1426）分别给出了~2.5 Ga和2.55 Ga的形成年龄,限制表壳岩形成时代老于2.55 Ga,推测为新太古代表壳岩.浅粒岩（HB1431）和紫苏石榴黑云斜长片麻岩（HB1435）中最老的碎屑锆石分别为2.46 Ga和2.51 Ga,可能还存在古元古代的碎屑锆石,表明它们都为古元古代表壳岩.上述结果进一步确定了怀安杂岩中发育两期表壳岩组合.变质辉长岩和片麻状英云闪长岩的全岩ε_Nd（t）、T_DM1和T_DM2分别为+2.19~+3.06、2.67~2.75 Ga和2.67~2.69 Ga,表明其物源区不存在较大规模的古老陆壳物质,新太古代是怀安地区主要陆壳生长期.变质辉长岩中~1.82 Ga变质锆石中较多具有正的ε_Hf（t）值,最高可达11.1,最可能的解释是古元古代变质过程存在地幔添加作用.锆石的O同位素分析显示区域上可能存在低δ18O的岩石,在古元古代变质过程中,可能存在低δ18O流体对锆石的改造.怀安杂岩和西部孔兹岩带中不同类型岩石的比例明显不同,但两者都同样发育新太古代和古元古代的双层地壳结构,怀安杂岩或许代表孔兹岩带剥蚀更深而出露的深部地壳部分.      

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,oxygen and strontium isotope geochemistry of Proterozoic carbonate rocks of the Vindhyan Basin,central India

Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ¹³C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ¹³C compositions. In the central Vindhyan section, the carbonates exhibit positive δ¹³C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ¹⁸O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ ¹⁸O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved ⁸⁷Sr/⁸⁶Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ¹³C values from Upper Vindhyan are characterized by lower ⁸⁷Sr/⁸⁶Sr values (0.7068±2) than those with negative δ¹³C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.     

黔东南平秋金矿成因研究:来自氢、氧、硫同位素的制约

黔东南地处江南造山带西南段雪峰隆起西南端,区内金矿床(点)广布,是湘黔金矿集中区的重要组成部分。平秋金矿是该区金矿床的典型代表,其矿体产于下江群番召组浅变质火山-沉积岩,严格受北东向断裂褶皱控制。为理清其成因,对平秋金矿床含矿石英脉中的石英包裹体进行了氢、氧同位素测试。结果显示,其δD为-51.3‰~-59‰,δ18OH2O-SMOW为4.46‰~8.16‰,表明平秋金矿成矿期流体以变质水为主。对成矿期黄铁矿的硫同位素分析结果表明,其δ34S值为-1.86‰~4.55‰,而围岩下江群浅变质岩中黄铁矿的δ34S值为9.63‰~13.56‰,二者相差巨大,表明矿床中硫不是直接来自于赋矿围岩。根据上述氢、氧、硫同位素测定结果并结合区域地质背景,本文认为平秋金矿的成矿流体和成矿物质源自下伏地层的变质脱水作用,成矿作用与加里东运动造成的变质变形有关。     

Hydrothermal flow systems in the Midcontinent Rift: oxygen and hydrogen isotopic studies of the North Shore Volcanic Group and related hypabyssal sills,Minnesota

Rift-related lavas of the North Shore Volcanic Group (NSVG) are intruded by plutonic rocks of the Duluth Complex along the unconformity between the NSVG and the underlying Proterozoic metasedimentary rocks (Animikie Group) and Archean volcano-sedimentary and plutonic rocks. Heat associated with the emplacement of the mafic intrusions generated fluid flow in the overlying plateau lavas. δ¹⁸O values for whole rocks from the NSVG and hypabyssal sills range from 5.5 to 17.7‰ and 5.3 to 11.5‰, respectively, and most values are higher than those considered “normal” for basaltic rocks (5.4 to 6.0‰). In general, there is a positive correlation between whole rock δ¹⁸O and water content, which suggests that elevated δ¹⁸O values are related primarily to secondary mineral growth and isotopic exchange during hydrothermal alteration and metamorphism. δ¹⁸O_H2O values computed from amygdule-filling minerals such as smectite, chlorite, and epidote found in low- to high-temperature metamorphic zones range from ∼−1 to 6‰ with an average value of ∼3‰. Smectite in the lower-grade zones gives computed δD_H2O values between −26 and −83‰, whereas epidote in the higher-grade zones gives δD_H2O values of −15 to 6‰. Fluid isotopic compositions computed from epidote and smectite values are suggestive of the involvement of at least two fluids during the early stages of amygdule filling. Fluid δD and δ¹⁸O values determined from epidote at the higher metamorphic grades indicate that seawater dominated the deeper portions of the system where greenschist facies assemblages and elevated δ¹⁸O values were produced in flow interiors, as well as margins. Smectite isotopic compositions suggest that meteoric water was predominant in the shallower portions of the system. The increase in δ¹⁸O values of massive flow interiors with depth is interpreted as a result of rock interaction with a fluid of constant oxygen isotopic composition with increasing temperature. The stable isotopic data are supportive of previous suggestions that seawater was involved in the hydrothermal system associated with the Midcontinent Rift. Although the origin of the seawater remains problematic, it appears that marine incursions may have occurred during the late stages of Portage Lake volcanism, and periodically thereafter.     

A reinterpretation of the crustal N‐isotope record: evidence for a 15N‐enriched Archean atmosphere?

A new compilation of N‐isotope and abundance data for metasedimentary rocks, and hyrdothermal micas that proxy for bulk crust, show systematic patterns. (1) δ¹⁵N values of kerogen in Precambrian cherts are more negative relative to siliciclastic counterparts, probably due to a mantle hydrothermal component. (2) There is a secular trend from average δ¹⁵N 15.3 ± 1.8‰ in Archean shales, through intermediate values in the Proterozoic, to Phanerozoic counterparts where δ¹⁵N averages +3.5‰. (3) Hydrothermal micas in metamorphic hydrothermal systems of Palaeozoic and Mesozoic age that proxy for crust have δ¹⁵N within the range of contemporaneous sedimentary rocks. (4) Hydrothermal micas track the secular trend of δ¹⁵N for kerogen from 2.7 Ga to the Phanerozoic. (5) Within Precambrian datasets δ¹⁵N does not increase with decreasing N content; accordingly, high δ¹⁵N values cannot stem either from metamorphism or form Rayleigh fractionation. (6) Previous studies show isotopic shifts during metamorphism are only +1 to +3‰ up to amphibolite facies. Values of 10–24‰ are attributed to a high δ¹⁵N Archean atmosphere, a residual signature of CI carbonaceous chondrites where δ¹⁵N is +30‰ to + 42‰.     

Channelized fluids in subducted continental crust: constraints from δD–δ18O of quartz and fluid inclusions in quartz veins from the Chinese Continental Scientific Drilling Project

Fluid inclusions hosted by quartz veins in high-pressure to ultrahigh-pressure (HP-UHP) metamorphic rocks from the Chinese Continental Scientific Drilling (CCSD) Project main drillhole have low, varied hydrogen isotopic compositions (δD?=??97‰ to??69‰). Quartz δ¹⁸O values range from??2.5‰ to 9.6‰; fluid inclusions hosted in quartz have correspondingly low δ¹⁸O values of??11.66‰ to 0.93‰ (T _h?=?171.2～318.8°C). The low δD and δ¹⁸O isotopic data indicate that protoliths of some CCSD HP-UHP metamorphic rocks reacted with meteoric water at high latitude near the surface before being subducted to great depth. In addition, the δ¹⁸O of the quartz veins and fluid inclusions vary greatly with the drillhole depth. Lower δ¹⁸O values occur at depths of ～900–1000 m and ～2700 m, whereas higher values characterize rocks at depths of about 1770 m and 4000 m, correlating roughly with those of wall-rock minerals. Given that the peak metamorphic temperature of the Dabie-Sulu UHP metamorphic rocks was about 800°C or higher, much higher than the closure temperature of oxygen isotopes in quartz under wet conditions, such synchronous variations can be explained by re-equilibration. In contrast, δD values of fluid inclusions show a different relationship with depth. This is probably because oxygen is a major element of both fluids and silicates and is much more abundant in the quartz veins and silicate minerals than is hydrogen. The oxygen isotope composition of fluid inclusions is evidently more susceptible to late-stage re-equilibration with silicate minerals than is the hydrogen isotope composition. Therefore, different δD and δ¹⁸O patterns imply that dramatic fluid migration occurred, whereas the co-variation of oxygen isotopes in fluid inclusions, quartz veins, and wall-rock minerals can be better interpreted by re-equilibration during exhumation.

Quartz veins in the Dabie-Sulu UHP metamorphic terrane are the product of high-Si fluids. Given that channelized fluid migration is much faster than pervasive flow, and that the veins formed through precipitation of quartz from high-Si fluids, the abundant veins indicate significant fluid mobilization and migration within this subducted continental slab. Many mineral reactions can produce high-Si fluids. For UHP metamorphic rocks, major dehydration during subduction occurred when pressure–temperature conditions exceeded the stability of lawsonite. In contrast, for low-temperature eclogites and other HP metamorphic rocks with peak metamorphic P–T conditions within the stability field of lawsonite, dehydration and associated high-Si fluid release may have occurred as hydrous minerals were destabilized at lower pressure during exhumation. Because subduction is a continuous process whereas only a minor fraction of the subducted slabs returns to the surface, dehydration during underflow is more prevalent than exhumation even in subducted continental crust, which is considerably drier than altered oceanic crust.     

Local distribution of oxygen isotopes and fluid exchange during genesis of the corundum-bearing rocks of Khitostrov Island

New data are presented on the distribution of oxygen isotopes and conditions of the local isotope equilibrium in high-Al rocks rocks of Khitostrov Island showing abnormally low δ¹⁸O values (below–25‰). The temperatures of isotope equilibrium are within 400–475°C. The minimum δ¹⁸O values have been registered in the in plagioclase, whereas the same phases in kyanite-bearing rocks lacking corundum demonstrate δ¹⁸O values usually 3–5‰ higher. The fluid δ¹⁸O value varies from–22 to–16‰ at 475 ± 15°C, from–18 to–23‰ at 425 ± 25°C, and from–17 to–22‰ at 380 ± 15°C. The results obtained do not require abnormal depletion of δ¹⁸O values owing to the infiltration of an external fluid under the Svecofennian transformations. The association of corundum-bearing rocks with the basic intrusions, the presence of zircon cores of older ages compared to these rocks, and the peculiarities of rock chemistry may be ascribed to the fact that lower crustal layers of ancient rocks depleted in δ¹⁸O before metamorphism were captured by basite melts.     

40Ar/39Ar and oxygen isotope studies of polymetamorphism from Tinos Island, Cycladic blueschist belt, Greece

Abstract Petrological, oxygen isotope and ⁴⁰Ar/³⁹Ar studies were used to constrain the Tertiary metamorphic evolution of the lower tectonic unit of the Cyclades on Tinos. Polyphase high-pressure metamorphism reached pressures in excess of 15 kbar, based on measurements of the Si content in potassic white mica. Temperatures of 450–500° C at the thermal peak of high-pressure metamorphism were estimated from critical metamorphic assemblages, the validity of which is confirmed by a quartz–magnetite oxygen isotope temperature of 470° C. Some ⁴⁰Ar/³⁹Ar spectra of white mica give plateau ages of 44–40 Ma that are considered to represent dynamic recrystallization under peak or slightly post-peak high-pressure metamorphic conditions. Early stages in the prograde high-pressure evolution may be documented by older apparent ages in the high-temperature steps of some spectra. Eclogite to epidote blueschist facies mineralogies were partially or totally replaced by retrograde greenschist facies assemblages during exhumation. Oxygen isotope thermometry of four quartz–magnetite pairs from greenschist samples gives temperatures of 440–470° C which cannot be distinguished from those deduced for the high-pressure event. The exhumation and overprint is documented by decreasing ages of 32–28 Ma in some greenschists and late-stage blueschist rocks, and ages of 30–20 Ma in the lower temperature steps of the Ar release patterns of blueschist micas. Almost flat parts of Ar–Ar release spectra of some greenschist micas gave ages of 23–21 Ma which are assumed to represent incomplete resetting caused by a renewed prograde phase of greenschist metamorphism. Oxygen isotope compositions of blueschist and greenschist facies minerals show no evidence for the infiltration of a δ¹⁸O-enriched fluid. Rather, the compositions indicate that fluid to rock ratios were very low, the isotopic compositions being primarily controlled by those of the protolith rocks. We assume that the fundamental control catalysing the transformation of blueschists into greenschists and the associated resetting of their isotopic systems was the selective infiltration of metamorphic fluid. A quartz–magnetite sample from a contact metamorphic skarn, taken near the Miocene monzogranite of Tinos, gave an oxygen isotope temperature of 555° C and calculated water composition of 9.1%. The value of δ¹⁸O obtained from this water is consistent with a primary magmatic fluid, but is lower than that of fluids associated with the greenschist overprint, which indicates that the latter event cannot be directly related to the monozogranite intrusion.     

Calcite–graphite isotope thermometry: a test for polymetamorphism in marble, Tudor gabbro aureole, Ontario, Canada

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 (δ¹³C_Cal–Gr) with independent petrological thermometers provides the following empirical calibration over the range 400–800°C: δ¹³C_Cal–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 δ¹³C_Cal–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.     

Zircon SHRIMP U–Pb dating,C and O isotopes for impure marbles from the Jiaobei terrane in the Sulu orogen: Implication for tectonic affinity

Middle Neoproterozoic carbonates are found in the western part of Shandong Pennisula (i.e., the Jiaobei terrane) that is located in the northwestern part of the Sulu orogen in east-central China. For the first time, a successful SHRIMP U–Pb dating, coupled with CL imaging, was conducted on two samples of impure marble from the Fenzishan Group in this tectonic unit. The results yield consistent ages of 786 ± 67 and 240 ± 44 Ma for igneous and metamorphic zircons, respectively. Positive δ¹³C values as high as +5.6‰ are measured for both pure and impure marbles, consistent not only with the worldwide Neoproterozoic limestones in connection with the Sturtian ice-age, but also with the marbles associated with UHP metamorphic eclogites in the Dabie orogen. O isotope fractionation between calcite and garnet from one sample gave a temperature of 680 °C, pointing to upper amphibolite-facies metamorphic conditions. These results indicate that protolith of the marbles is a kind of limestone that was synchronously deposited with volcaniclastic rocks in the mid-Neoproterozoic rift basin of continental margin. Like the UHP metamorphic rocks in the Dabie-Sulu orogenic belt, both mid-Neoproterozoic magmatism and Triassic metamorphism are recorded in the impure marbles. Therefore, protolith of the impure marbles corresponds to the sedimentary limestone of rift basin developed during the mid-Neoproterozoic breakup of supercontinent Rodinia, but it was the sedimentary cover along the northern margin of the South China Block prior to its Triassic subduction. The occurrence of the mid-Neoproterozoic limestone with the Triassic metamorphism in the southern margin of the North China Block thus indicates tectonic overthrust by a crustal detachment between the sedimentary cover and the Precambrian basement during the continent subduction. As a result, the marbles in affinity to the South China Block were northward thrusted over the basement of the North China Block.     

Silicate oxygen isotope geochemistry: History,principles, techniques,and application to petrological problems

The importance of oxygen isotope geochemistry in studies of terrestrial and extra-terrestrial silicate rocks was recognized nearly sixtyeight years ago soon after the discovery of O¹⁸ and O¹⁷. As early as 1934, the significance of oxygen isotope variations in rocks and minerals was stressed by Russian geochemists who also pioneered the discipline of silicate oxygen isotope geochemistry. It is now known that processes involving isotopic interaction between rock and water, magmatic differentiation, and metamorphic recrystallization fractionate oxygen isotopes in the lithosphere. δO¹⁸ (the conventional notation for reporting O¹⁸/O¹⁶ ratios in rocks and minerals) is highest in sedimentary rocks (17 to 35 ‰) and lowest in igneous rocks (4 to 12‰). Metamorphic rocks have intermediate values. δO¹⁸ in mafic minerals (1 to 8‰) is lower than in felsic minerals (8 to 16‰). In igneous and metamorphic rocks, quartz is most enriched in O¹⁸ (10 to 16‰) and magnetite the least (1 to 2‰). An important application of O¹⁸/O¹⁶ techniques is in geothermometry, where these are capable of elucidating several petrological processes.