Oxygen isotopic fractionation in the system quartz-albite-anorthite-water

Oxygen isotopic fractionations have been determined between quartz and water, albite and water, and anorthite and water at temperatures from 300 to 825°C, and pressures from 1.5. to 25 kbar. The equilibrium quartz-feldspar fractionation curves can be approximated by the following equations: 1000ln α_Q?PI = (0.46 + 0.55β)10⁶T^?2 + (0.02 + 0.85β) between 500 and 800°C 1000ln α_Q?PI = (0.79 + 0.90β)10⁶T^?2 — (0.43 ? 0.30β) between 400 and 500°C where β is the mole-fraction of anorthite in plagioclase.Application of these isotopic thermometer calibrations to literature data on quartz and feldspar gives temperatures for some metamorphic rocks which are concordant with quartz-magnetite temperatures. Plutonic igneous rocks typically have quartz-feldspar fractionations which are substantially larger than the equilibrium values at solidus temperatures, indicating substantial retrograde exchange effects.     

18O/16O ratios of anorthosites and related rocks from the Rogaland Complex (SW Norway)

The South Rogaland Complex (South Western Norway) consists of several anorthositic intrusions emplaced in granulite facies metamorphic rocks. The anorthosites and related norites and jotunites have δ ¹⁸O values of 5.2 to 7‰ suggesting a mantle origin for these rocks, in agreement with the strontium isotopic evidence. The acidic rocks, mostly charnockitic, associated with the anorthosites have similar δ ¹⁸O values and thus a comagmatic relation between these two rock types is inferred. Small departures from mantle values are explained in terms of crustal contamination by surrounding gneisses that have δ ¹⁸O values between 4.3 and 10‰ Locally, this corresponds to important anatexis as has been suggested for the Farsund charnockite on the basis of strontium isotope and REE geochemistry. The isotopic temperatures calculated from the isotopic fractionations are in the range 500°–700° C, lower than the orthomagmatic temperatures and probably due to subsolidus isotopic exchange during the slow cooling of these plutonic rocks, either during a late magmatic deuteric stage or during a slow, postorogenic ascent under wet conditions.     

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.     

Oxygen isotope study of metamorphic and granitic rocks of the Yanai district in the Ryoke belt,Japan

¹⁸O/¹⁶O ratios have been obtained for 134 whole-rocks and minerals from metamorphic and granitic rocks of the Yanai district in the Ryoke belt, Southwest Japan. The ¹⁸O/¹⁶O ratios of pelitic rocks of the marginal metamorphic zone decrease progressively with increasing metamorphic grade. In the gneiss-granite complex (zone of migmatite [1]), the most characteristic feature of the rocks is that oxygen isotopic homogenization proceeds on both local and regional scales in parallel with “granitization” or chemical homogenization. Granitic rocks of various origin are fairly uniform in isotopic composition with δ ¹⁸O of quartz of 12 to 14‰ (SMOW) and δ ¹⁸O of biotite of 7 to 9‰ and are about 3 to 4‰ enriched in ¹⁸O compared to other Cretaceous granites of non-metamorphic terranes in Japan. The high ¹⁸O/¹⁶O ratios of granitic rocks of this district were discussed in relation to the ¹⁸O-depletion in metasediments. Oxygen isotopic fractionations among coexisting minerals from various rock-types of the gneiss-granite complex indicate that these minerals were formed under near isotopic equilibrium at a temperature of about 600 to 700° C. Some abnormal fractionations of quartz-biotite pairs also were obtained for rocks which had undergone a progressive ¹⁸O-depletion or ¹⁸O-enrichment. This is due to high resistivity of quartz and contrastive susceptibility of biotite to isotopic exchange during metamorphism and “granitization”.     

The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota

The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ¹⁸O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ¹⁸O–δ⁵⁶Fe variations in magnetite is a strong increase in δ¹⁸O_Mt and a mild decrease in δ⁵⁶Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

Oxygen and hydrogen isotopic studies of ore deposition and metamorphism at the Raul mine,Peru

The volcano-sedimentary sequence at the Raul mine, central Peru, consists of andesitic volcanics, graywackes, and siltstones, and has been metamorphosed to the upper greenschist-lower amphibolite facies at temperatures of 400–500°C. Isotopic data (O and H) have been collected from: (a) quartz and magnetite from stratiform ores, (b) amphiboles from amphibolite units that host stratiform ores, (c) calcite from late veins, (d) detrital quartz from graywackes, and (e) whole rocks.Interunit differences in quartz and magnetite δ¹⁸O values suggest that these minerals have resisted isotopic exchange during metamorphism, and that quartz-magnetite isotopic temperatures (380–414°C) represent primary formational temperatures. Calculated δ¹⁸O values of water in equilibrium with quartz and magnetite range from 9.1 to 12.6%..Amphibole δ¹⁸O and δD values show no interunit differences and suggest that the amphiboles have exchanged isotopes with a large metamorphic fluid reservoir. Calculated δ¹⁸O_H2O and δD_H2O values range from 8 to 12%. and ?3 to +42%., respectively.δ¹⁸O_H2O values calculated from δ¹⁸O calcite and fluid inclusion filling temperatures range from 7.5 to 10%.. Water extracted from fluid inclusions in calcite has a δD value of ?20%..δ¹⁸O values of metamorphosed graywackes and volcanic sediments are not atypical, but andesitic lavas are ¹⁸O-rich (8–10%.) compared to normal andesites.Waters involved in ore deposition, metamorphism, and late vein formation at Raul are all thought to have a common source, principally seawater. The δ¹⁸O_H2O and δD_H2O values could be produced by evaporation of seawater, shale ultrafiltration, and isotopic exchange with host rocks during deep circulation through the volcano-sedimentary pile.A model is proposed whereby coastal ocean water is restricted from the open sea by volcanic island arcs, and subsequently undergoes evaporation. Circulation of this water is initiated by heat associated with seafloor volcanism. ¹⁸O-enrichment in andesites may be produced by isotopic exchange with high ¹⁸O waters at elevated temperatures and sufficiently high water/rock ratios.     

The geochemistry of the stable isotopes of silicon

One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of ^δ30Si found is 6.2%., centered on the mean of terrestrial mafic and ultramafic igneous rocks, δ³⁰Si = ?0.4%.. Igneous rocks show limited (1.1%.) variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly $\text{1}\text{3}$ the magnitude of concomitant oxygen isotopic fractionations at 1150°C. In both igneous minerals and rocks, δ³⁰Si shows a positive correlation with silicon content, as does δ¹⁸O. Opal from both sponge spicules and sinters is light, with $\text{}\text{?}\text{gd}{}^{30}\text{Si}\text{= ?2.3}$ and ?1.4%., respectively. Large ^δ30Si values of both positive and negative sign are reported for the first time from clay minerals (?2.3 to +1.8%.), opaline phytoliths (?1.4 to +2.8%.), and authigenic quartz (+ 1.4%.). All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of ≈3.5%. is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in ²⁸Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic δ³⁰Si variations. Chert ^δ30Si values are largely inherited, but the primary opal ^δ30Si values can be modified by isotopic equilibration of silicate silicon and dissolved silicon during the transformation of opal into quartz.     

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.     

Stable Fe isotope fractionations produced by aqueous Fe(II)-hematite surface interactions

Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)_aq - oxide interaction will produce low δ⁵⁶Fe values for Fe(II)_aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ⁵⁶Fe Fe(II)_aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ⁵⁶Fe aqueous Fe(II) in many natural systems.     

Extreme 18O-enriched volcanics and 18O-evolved marine water,Aljustrel, Iberian Pyrite Belt: transition from high to low Rayleigh number convective regimes

Quartz-eye keratophyric tuffs at Aljustrel, S. Portugal, Iberian Pyrite Belt possess unusually high, uniform whole rock δ-values up to 18.1%. with a mean of 16.7 ± 0.7%.. Because the quartz eye cores have δ¹⁸O 12.0 to 13.5%. the felsic tuffs may have had an original whole rock oxygen isotope composition of 10 to 11%. The deduced enrichments of up to +8%. in keratophyric derivatives is attributed to isotope exchange with abundant marine water under temperatures which diminished to ≤ 100°C, during thermally driven convective cooling. The isotopic uniformity requires elevated permeability of ～ 10^?8 cm², such that the second critical Rayleigh number was exceeded, and drifting, non steady state convection cells dominated, with relatively smooth thermal structures.In mineralised counterparts of the tuffs beneath the Feitais-Estacao Zn-Pb-Cu massive sulphide orebodies, whole rock δ-values are ~12%. and quartz (13.3–15.4%.)-chlorite (3.2–6.3%.) fractionations correspond to temperatures of 220–270°C, and a calculated fluid δ¹⁸O of 1.4 to 5.7%. This local isotopic overprinting in vent domains of the regionally high ¹⁸O was induced by a stable, second stage convective regime imposed by drastic reduction of permeability accompanying capping of the geothermal discharge by hydrothermal cherts, and/or progressive spilitisation of the tuffs. At lower water/rock coupled with higher temperatures, the recirculating marine water underwent variable ¹⁸O enrichment up to 5.7%. by exchange with the high ¹⁸O tuffs. An upwards increase in δ¹⁸O quartz and δ-quartz reflects progressive cooling of the geothermal discharge from 15.4%. 270°C in the stockwork, through 18.3%. 220–240°C in the orebody, to 20.1%. 110–130°C in overlying hydrothermal cherts, probably induced by entrainment of ambient marine bottom water in sub-seafloor aquifers.     

Hydrogen and oxygen isotope ratios in nodular and bedded cherts

Hydrogen and oxygen isotopic compositions of cherts (δD for hydroxyl hydrogen in the chert, δ¹⁸O for the total oxygen) have been determined for a suite of samples from the central and western United States. When plotted on a δD-δ¹⁸O diagram, Phanerozoic cherts define domains parallel to the meteoric water line which are different for different periods of geologic time. The elongation parallel to the meteoric water line suggests that meteoric waters were involved in the formation of many cherts.The existence of different chert δ-values for different geologic times indicates that once the granular microcrystalline quartz of cherts crystallizes its isotopic composition is preserved with time. An explanation for the change with time of the isotopic composition of cherts involving large changes with time in the isotopic composition of ocean water is unlikely since δ¹⁸O of the ocean would have had to decrease by about 3‰between Carboniferous and Triassic time and then increase about 5%.` from Triassic to Cretaceous time. Such isotopic changes cannot be accounted for by extensive glaciation, sedimentation of hydrous minerals, or input of water from the mantle into the oceans.The variation with time of the chert δ-values can be satisfactorily explained in terms of past climatic temperature fluctuations if the chert-water isotope fractionation with temperature is approximated by 1000 lnα = 3.09 × 10⁶T^?2 – 3.29. Crystallization temperatures so inferred suggest that the average climatic temperatures for the central and western U.S. decreased from about 34 to 20°C through the Paleozoic, increased to 35–40°C in the Triassic, and then decreased through the Mesozoic to Tertiary values of about 17°C. A few data for the Precambrian suggest the possibility that Earth surface temperatures may have reached about 52°C at 1.3 b.y. and about 70°C at 3 b.y.     

Oxygen isotope compositions and magmatic epidote from two contrasting metaluminous granitoids,NE Brazil

Oxygen isotope compositions of mineral separates were determined from two metaluminous granitoids (Emas and São Rafael plutons) from northeastern Brazil. The I-type Emas pluton has high δ¹⁸O (WR) values (11.5–11.8‰), whereas the São Rafael pluton has low δ¹⁸O (WR) values (7.5–8.1‰), but Sr and Nd are characteristics of S-type granitoids. Measured mineral–mineral fractionations suggest continuous sub-solidus inter-mineral isotope exchange among all minerals except zircon. There is a large and consistent quartz–epidote fractionation that gives apparent temperatures that are much lower than anticipated closure temperatures for epidote. Oxygen isotope fractionation between natural zircon and magmatic epidote is opposite to that predicted from theoretical determinations, as δ¹⁸O (epidote) <δ¹⁸O (zircon). An empirical calibration based on these results would suggests a closure T for oxygen in epidote of ~500 °C and Δ(qtz–epi) ~5.19 at 500 °C.     

Argillization processes at the El Berrocal analogue granitic system (Spain): mineralogy,isotopic study and implications for the performance assessment of radwaste geological disposal

The El Berrocal granite/U-bearing quartz vein (UQV) system has been studied as a natural analogue of a high-level radioactive waste repository. The main objective was to understand the geochemical behaviour of natural nuclides under different physicochemical conditions. Within this framework, the argillization processes related to fracturing and formation of the uranium–quartz vein were studied from a mineralogical and isotopic standpoint in order to establish their temperatures of formation and thus complete the geothermal history of the system. For this purpose, δ¹⁸O values were determined for pure mineral from the unaltered granite and quartz from the uranium–quartz vein, as well as for mixture samples from the hydrothermally altered granite (sericitised granite) and clayey samples from fracture fillings, including the clayey walls of the uranium–quartz vein. The isotopic signature of quartz from the uranium–quartz vein and the monophasic nature of its fluid inclusions led us to conclude that the isotopic signature of water in equilibrium with quartz was approximately in the range from −8.3‰ to −5.7‰ V-SMOV, its temperature of formation being around 85–120 °C. The δ¹⁸O values of pure sericite from the hydrothermally altered granite, calculated by means of the oxygen fraction molar method, indicate that its temperature of formation, in equilibrium with the aforementioned waters, is also in the range from 70 °C to approximately 120 °C. Clays from fracture fillings and clayey walls of the uranium–quartz vein are usually mixtures, in different proportions, of illite, approximately formed between 70 and 125 °C; two generations of kaolinite formed at approximately 90–130 °C and at around 25 °C, respectively; smectite, formed at ≤25 °C; and occasionally palygorskite, formed either between 30 and 45 °C or 19 and 32 °C, depending on the fractionation equation used. These data suggest that sericite from the hydrothermally altered granite, quartz from the uranium–quartz vein, illite and the first generation of kaolinite from the fracture fillings resulted from the same hydrothermal process affecting the El Berrocal granite in relation to fracturing. Under certain physicochemical conditions (T≈100 °C, pH≈8 and log [H₄SiO₄] between −4 and −3), illite and kaolinite can be paragenetic. As a result of weathering processes, smectite was formed from hydrothermal illite and inherited albite under alkaline weathering, while the second generation of kaolinite was formed from smectite, under acid conditions and close to the sulphide-rich uranium–quartz vein. Palygorskite is an occasional mineral formed probably either during the thermal tail of the above-described hydrothermal process or during weathering processes. In both cases, palygorskite must have formed from alkaline Si–Mg-rich solutions. Finally, these data and processes are discussed in terms of natural analogue processes, drawing some implications for the performance assessment of a deep geological radwaste repository (DGRR).     

Fluid inclusion and sulfur isotope thermometry of the Inkaya (Simav-Kütahya) Cu-Pb-Zn-(Ag) mineralization, NW TURKEY

The Inkaya Cu-Pb-Zn-(Ag) mineralization, located about 20 km west of the Simav (Kütahya-Turkey), is situated in the northern part of the Menderes Massif Metamorphics. The mineralization is located along an E-W trending fault in the Cambrian Simav metamorphics consisting of quartz-muscovite schist, quartz-biotite schist, muscovite schist, biotite schist and the Ar?kayas? formation composed of marbles. Mineralized veins are 30–35 cm in width. The primary mineralization is represented by abundant galena, sphalerite, chalcopyrite, pyrite, fahlore and minor amounts of cerussite, anglesite, digenite, enargite, chalcocite, covellite, bornite, limonite, hematite and goethite with gangue quartz. Fluid inclusion studies on the quartz samples collected from the mineralized veins indicate that the temperature range of the fluids is 235°C to 340°C and the salinities are 0.7 to 4.49 wt. % NaCl equivalent. The wide range of homogenization temperatures indicates that two different fluid generations were trapped in quartz. Sulfur isotope studies of the sulfide minerals showed that all of the δ ³⁴S values are between ?2.1 and 2.6 per mil. These values are a typical range for hydrothermal sulfide minerals that have sulfur derived from a magmatic source. Pyrite-galena and pyrite-chalcopyrite sulfur isotope fractionation is consistent with an approach to isotopic equilibrium, and calculated temperatures are 254.6 and 277.4°C for pyrite-galena and 274.7°C for pyrite-chalcopyrite. The microthermometric data and sulfur isotope thermometry indicate the existence of a hydrothermal fluid that circulated along the fault crossing the Simav metamorphics and Ar?kayas? formation. Fluid inclusion and sulfur isotope thermometry can be used in combination with ore petrographical and geological information to provide site-specific targets for meso-hypothermal metal concentrations.     

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.     

Stable isotope geochemistry of deep sea cherts

Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. δ¹⁸O of chert ranges between 27 and 39%. relative to SMOW, δ¹⁸O of porcellanite—between 30 and 42%.. The consistent enrichment of opal-CT in porcellanites in ¹⁸O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases.δ¹⁸O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975) indicates the possibility of δ¹⁸O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of δ¹⁸O values, increasing diagenesis being reflected in a lowering of δ¹⁸O. Drusy quartz has the lowest δ¹⁸O values.On-land exposed cherts are consistently depleted in ¹⁸O in comparison to their deep sea time equivalent cherts.Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. δD of this water ranges between ?78 and ?95%. and is not a function of δ¹⁸O of the cherts (or the temperature of their formation).     

Biogeochemical implications of the isotopic equilibrium fractionation factor between the oxygen atoms of acetone and water

Carbonyl oxygens of organic molecules undergo isotopic exchange with water during reversible hydration reactions. The equilibrium isotopic fractionation factors between the carbonyl oxygen of acetone and water at 15°, 25°, and 35°C are 1.028, 1.028, and 1.026 respectively. The differences between the δ¹⁸O values of the carbonyl oxygen of acetone and of the water with which it is in equilibrium are similar to the differences that have been observed between the δ¹⁸O values of cellulose and the water used in its synthesis by a variety of aquatic plants and animals. Additionally, the identity of the acetone-water fractionation factors at 15° and 25°C parallels the observation that the difference between the δ¹⁸O values of cellulose and water shows no temperature dependence for individual species of plants grown over the same temperature range. These results are discussed in relation to the proposal that the oxygen isotopic relationship between cellulose and water is established by isotopic exchange occurring during the hydration of carbonyl groups of the intermediates of cellulose synthesis.     

Oxygen isotope study of quartz-Al2SiO5 pairs from the Mica Creek area, British Columbia: implications for the recovery of peak metamorphic temperatures

Oxygen isotope analyses of quartz-Al₂SiO₅ pairs have been made for samples from the Mica Creek area, British Columbia. We have analysed quartz–kyanite nodules and quartz–kyanite and quartz–sillimanite in multiphase pelitic rocks from the staurolite–kyanite, kyanite, and sillimanite zones. Apparent temperatures calculated from oxygen isotopic fractionation range from 555 °C (staurolite–kyanite zone) to 695 °C (sillimanite zone). Temperatures from the quartz–kyanite nodules range from 630 to 675 °C. Some of the nodules show isotopic disequilibrium. Most of the results confirm predictions that bimineralic rocks will yield an estimate of peak metamorphic temperatures, when the less abundant mineral (an aluminium silicate) is the slower oxygen diffuser. Using cooling rates of 10–100 °C Ma^?1 for the multiphase rocks, measured crystal sizes and modes, the Fast Grain Boundary diffusion model with ‘wet’ diffusion data (P_H2O?1.0 kbar) yields predicted apparent temperatures which are generally lower than the measured apparent temperatures. The agreement is improved if slower diffusion coefficients are used. This suggests that f (H₂O) during cooling was lower than that of the hydrothermal experiments and thus that there was little interaction with aqueous fluids of internal or external origin to modify the isotopic compositions. The measured apparent isotopic temperatures and apparent garnet–biotite Fe–Mg exchange temperatures show very poor agreement for the sillimanite zone samples, with the garnet–biotite Fe–Mg exchange temperatures generally higher than the oxygen isotope temperatures. Compared with the other calibrations that we tested the measured apparent temperatures using the Sharp calibration show the best agreeement with recently published P–T grids, although some variability in agreement is expected due to variable f (H₂O) during cooling.     

Preservation of oxygen isotope compositions in granulites from Northwestern Canada and Enderby Land,Antarctica: implications for high-temperature isotopic thermometry

 Preservation of high-temperature mineral isotopic compositions is necessary for successful high-temperature isotopic thermometry. Other requirements include large fractionations between constituent minerals, well-calibrated equilibria, carefully designed sampling strategies and data handling techniques that quantitatively account for retrograde exchange. Here, we apply isotopic thermometry and data handling techniques to calculate and contrast mineral-pair apparent temperature data and observed closure temperature data (T _c-observed) (cf. Farquhar et al. 1993) for the very high temperature (>900°C), dry granulites of the Taltson Magmatic Zone of Northwestern Canada and the Napier Complex of Enderby Land, Antarctica. The isotopic compositions of garnet grains from both terrains reflect high temperature conditions (>950°C) and point to this mineral as an excellent candidate for isotopic thermometry. The isotopic compositions of quartz, pyroxene, ilmenite and magnetite indicate that they equilibrated to lower temperature conditions (<900°C) due to faster rates of oxygen diffusion in these minerals, possibly enhanced by exsolution and ductile deformation, compared with garnet. Our temperature data for garnet and pyroxene are ≈200°C higher than is possible to explain by existing “wet” diffusion data, but is consistent with “dry” diffusion data, suggesting that the extremely dry nature of these rocks may have played a significant role in the preservation of high-temperature isotopic compositions. Both quartz and magnetite exhibit subgrain features, indicative of ductile deformation. Quartz-magnetite temperatures from the Napier complex are similar to those inferred for a late (D3) deformation and are lower than those predicted by “dry” diffusion data. We infer that the quartz-magnetite isotopic fractionations reflect deformation-enhanced exchange that accompanied D3. Garnet in these same samples did not undergo ductile deformation and did not exchange oxygen with coexisiting phases during cooling. This may reflect strain partitioning between less easily deformed, low abundance garnet and more easily deformed matrix quartz and magnetite. The resistance of garnet to ductile deformation in these rocks is a second reason why garnet is suitable for isotopic thermometry. Received: 6 February 1996 / Accepted: 25 April 1996