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.     

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.     

角闪石族矿物的氧同位素分馏

利用增量方法和同位素交换技术,对角闪石族矿物的氧同位素分馏进行了理论计算和实验测定。理论结果表明,不同化学成分的角闪石之间存在一定的氧同位素分馏,其13O富集顺序为:钠闪石>蓝闪石>铁闪石>阳起石=镁铁门石≥直闪石≥透闪石>普通角闪石>铝直闪石>韭闪石。高温条件下(>500℃),角闪石相对于水亏损¹⁸O达1‰至3‰。实验进行在有少量流体存在的条件下,温度为520℃至680℃。所确定的方解石-透闪石氧同位素分馏系数与理论计算值在误差范围内完全一致。理论和实验确定的石英-透闪石分馏曲线均显着低于已知的经验校准曲线,反映了变质岩中含角闪石矿物集合体内部的退化同位素再平衡。     

Oxygen isotopic compositions of IVA iron meteorites: implications for the thermal evolution derived from in situ ultraviolet laser microprobe analyses

Oxygen isotopic compositions of silicate inclusions in IVA iron meteorites have been measured with an in situ UV laser microprobe technique. The homogeneity of oxygen isotopic compositions within and among individual mineral grains has also been examined. Oxygen isotope fractionations between coexisting mineral pairs were utilized in oxygen isotope thermometry. Our measured Δ¹⁷O values, ranging from 0.97 to 1.25‰, are characteristic of a single reservoir and fully confirm the oxygen isotopic similarity between IVA irons and L/LL chondrites. Steinbach and São João Nepomuceno, containing inclusions of two silicate minerals in mutual contact, exhibit a mass-dependent fractionation of ¹⁸O/¹⁶O between tridymite and bronzite with apparent oxygen isotopic heterogeneity. The SiO₂-bearing member, Gibeon, gives homogeneous oxygen isotopic compositions without detectable fractionation of ¹⁸O/¹⁶O between tridymite and quartz. Oxygen isotope equilibrium temperatures are estimated for coexisting tridymite and bronzite in the same sample slabs or clusters in Steinbach and São João Nepomuceno. The fractionations of ¹⁸O/¹⁶O between bronzite and tridymite range from 1.6 to 2.3‰ in different sample slabs or clusters. On the basis of the closure temperature concept, cooling rates are estimated at approximately 20 to 1000°C/Myr between 800 and 1000°C, a range of temperatures not accessible to other cooling rate methods. Using the Fast Grain Boundary diffusion model, we have demonstrated that significant oxygen heterogeneity both in tridymite and bronzite is probably due to isotope exchange during cooling between minerals with various grain sizes and mineral abundances in different regions of the samples. The new estimates of cooling rate by oxygen isotope thermometry refine previous cooling curves of IVA irons and support the breakup-reassembly model for the IVA parent body.     

The role of the grain boundary at chemical and isotopic fronts in marble during contact metamorphism

Carbon and oxygen isotopic profiles around a low pressure metasomatic wollastonite reaction front in a marble of the Hida metamorphic terrain, central Japan, display typical metamorphic fluid-enhanced isotopic zonations. Isotopic profiles obtained from detailed microscale analyses perpendicular to the chemical reaction front in calcite marble show that diffusion-enhanced isotopic exchange may control these profiles. Carbon and oxygen isotopic behaviour in grain boundaries is remarkably different. Oxygen isotopic troughs (¹⁸O depleted rims) around the calcite-grain boundaries are widely observed in this contact aureole, demonstrating that diffusion of oxygen in calcite grain boundary dominates over lattice diffusion in calcite. In contrast, no difference is observed in carbon isotopic profiles obtained from grain cores and rims. There is thus no specific role of the grain boundary for diffusion of carbonic species in the metamorphic fluid during transportation. Carbon chemical species such as CO₂ and CO₃ ions in metamorphic fluid migrate mainly through lattice diffusion. The carbon and oxygen isotope profiles may be modelled by diffusion into a semi-infinite medium. Empirically lattice diffusion of oxygen isotopes is almost six times faster than that of carbon isotopes, and oxygen grain-boundary diffusion is ten times faster than oxygen lattice diffusion. Oxygen isotopic results around the wollastonite vein indicate that migration of the metamorphic fluid into calcite marble was small and was parallel to the aquifer. From the stability of wollastonite and the attainment of oxygen isotopic equilibrium, we suggest that diffusion of oxygen occurred through an aqueous fluid phase. The timescale of formation of the oxygen isotopic profile around the wollastonite vein is calculated to be about 0.76 × 10⁶ years using the experimentally determined diffusion constant. Received: 14 January 1997 / Accepted: 23 April 1998     

Oxygen and hydrogen isotope geochemistry of gneisses associated with ultrahigh pressure eclogites at Shuanghe in the Dabie Mountains

The oxygen and hydrogen isotope compositions of minerals and whole rock were determined for two types of gneiss (biotite gneiss and granitic gneiss) associated with ultrahigh pressure (UHP) eclogites in the Shuanghe district of the eastern Dabie Mountains. There are significant differences in δ¹⁸O between the two gneisses: the UHP biotite gneiss varying from −4.3‰ to 10.6‰ similar to the associated eclogites, whereas the non-UHP granitic gneiss ranges only from −3.8‰ to 1.2‰. The δD values are similar in the two gneisses with −37 to −64‰ for epidote/zoisite, −92 to −83‰ for amphibole, and −63 to −109‰ for biotite/phengite. Hydrogen isotope disequilibrium among the coexisting hydroxyl-bearing minerals is ascribed to retrograde exchange subsequent to amphibolite-facies metamorphism. Oxygen isotopic equilibrium has been preserved among various minerals in both gneisses regardless of the large variation in rock δ¹⁸O. Oxygen isotopic geothermometers yield different but regular temperatures corresponding to the closure temperatures of oxygen diffusion in the minerals. The metamorphic temperatures of both eclogite facies and amphibolite facies have been recovered in mineral pairs from the biotite gneiss. The isotopic temperatures for the granitic gneiss are mostly in accordance with amphibolite-facies metamorphism. However, high temperatures of 550 to 650 °C are obtained from those minerals resistant to retrograde oxygen isotope exchange, implying that the granitic gneiss may have experienced higher temperature metamorphism than expected from petrologic thermometers. The ¹⁸O-depletion of both gneisses is interpreted to result from meteoric-hydrothermal exchange before/during plate subduction. Therefore, the measured δ¹⁸O values of the gneisses reflect the oxygen isotope compositions of their protoliths prior to the UHP metamorphism. It is inferred that the UHP unit is in foreign contact with the non-UHP unit like a tectonic melange, but both of them experienced the two common stages of geodynamic evolution: (1) ¹⁸O-depletion prior to the UHP metamorphism, (2) uplifting since the amphibolite-facies metamorphism. Received: 5 May 1998 / Accepted: 27 August 1998     

On the Direction and Magnitude of Oxygen Isotope Fractionation Between Calcite and Aragonite at Thermodynamic Equilibrium

Oxygen isotope fractionation factors between calcium carbonates and water have been applied to ancient marine geochemistry principally for the purpose of geothermometry. The problem was encountered, however, with respect to the direction and magnitude of oxygen isotope fractionation between calcite and aragonite at thermodynamic equilibrium. This basically involves sound understanding of both thermodynamics and kinetics of oxygen isotope fractionation between inorganically precipitated carbonate and water at low temperatures. Thus the crucial issues are to acknowledge the processes of chemical reaction and isotopic exchange during precipitation of CaCO₃ minerals in solution, the kinetic mechanism of isotope equilibrium or disequilibrium, the effect of polymorphic transition from metastable aragonite to stable calcite under hydrous or anhydrous conditions, and the presence or absence of isotope salt effect on oxygen isotope exchange between carbonate and water in response to the hydrous or anhydrous conditions at thermodynamic equilibrium. Because good agreements exist in carbonate–water oxygen isotope fractionation factors between theoretical calculations and experimental determinations, it is encouraging to applying the thermodynamic and kinetic data to isotopic paleothermometry and geochemical tracing.     

Synthesis of In‐House Produced Calibrated Silver Phosphate with a Large Range of Oxygen Isotope Compositions

The large range of stable oxygen isotope values of phosphate‐bearing minerals and dissolved phosphate of inorganic or organic origin requires the availability of in‐house produced calibrated silver phosphate of which isotopic ratios must closely bracket those of studied samples. We propose a simple protocol to synthesise Ag₃PO₄ in a wide range of oxygen isotope compositions based on the equilibrium isotopic fractionation factor and the kinetics and temperature of isotopic exchange in the phosphate–water system. Ag₃PO₄ crystals were obtained from KH₂PO₄ that was dissolved in water of known oxygen isotope composition. Isotopic exchange between dissolved phosphate and water took place at a desired and constant temperature into PYREX? tubes that were placed in a high precision oven for defined run‐times. Samples were withdrawn at desired times, quenched in cold water and precipitated as Ag₃PO₄. We provide a calculation sheet that computes the δ¹⁸O of precipitated Ag₃PO₄ as a function of time, temperature and δ¹⁸O of both reactants KH₂PO₄ and H₂O at t = 0. Predicted oxygen isotope compositions of synthesised silver phosphate range from ?7 to +31‰ VSMOW for a temperature range comprised between 110 and 130 °C and a range of water δ¹⁸O from ?20 to +15‰ VSMOW.     

An empirical estimate of the diffusion rate of oxygen in diopside

The intracrystalline diffusion rate of oxygen in diopside was constrained based on natural isotopic variations from a granulite facies marble from Cascade Slide, Adirondacks (New York, USA). The oxygen isotope compositions of the diopsides, measured as a function of grain size, are nearly constant (20.9 ± 0.3‰ vs. SMOW) over the entire measured size range (0.3–3.2 mm diameter). The δ¹⁸O values of the cores of calcite grains are 23.0‰. Temperature estimates based on the Δ¹⁸O(calcite-diopside) are 800d?C, in agreement with the highest previous thermometric estimates for these rocks. The lack of isotopic variation in the diopsides as a function of grain size requires that the oxygen intracrystalline diffusion rate in diopside from the Adirondack samples was very slow. The maximum diffusion rates (D_800d?C parallel to the c-axis) were calculated with an infinite reservoir model (IRM) and a finite reservoir model (FRM) that incorporates mineral modal abundances and initial isotopic variations. For an assumed activation energy (Q) = 100 kJ/mol, the IRM diffusion rate estimate of 1.6 times 10^-20cm²/s is two orders of magnitude faster than from the FRM; at Q=500kJ/mol, the D_800d?C estimate for both methods is c. 5.6 times 10^-20 cm²/s. The present results require that a hydrothermal fluid significantly enhances the diffusion rate of oxygen in diopside if previous data are correct. The δ¹⁸O(SMOW) and δ¹³C(PDB) values of the calcite, measured in situ with a CO₂ laser, are 22.9 ± 0.3, 0.1±0.3‰ in the grain cores, 22.1 ±0.3, 0.2 ±0.1‰ at the grain boundaries and 21.7 ±0.4, -0.6±0.1‰ abutting diopside grains. The δ¹⁸O and δ¹³δC values measured conventionally are: crystal cores, 22.96, -0.95‰; abutting diopside grains, 22.38, -0.93‰; bulk, 22.79, -0.95%. Use of the bulk δ¹⁸O(calcite) values for thermometry yields unreasonably high temperatures. The lower δ¹⁸O values at the calcite grain boundaries are not due to retrograde diffusional exchange with the diopside, they are thought to be a result of a late retrograde fluid infiltration.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

O and H diffusion in uraninite: Implications for fluid-uraninite interactions, nuclear waste disposal, and nuclear forensics

Diffusion coefficients for oxygen and hydrogen were determined from a series of natural uraninite-H₂O experiments between 50 and 700 °C. Under hydrous conditions there are two diffusion mechanisms: (1) an initial extremely fast-path diffusion mechanism that overprinted the oxygen isotopic composition of the entire crystals regardless of temperature and (2) a slower volume-diffusive mechanism dominated by defect clusters that displace or eject nearest neighbor oxygen atoms to form two interstitial sites and two partial vacancies, and by vacancy migration. Using the volume diffusion coefficients in the temperature range of 400-600 °C, diffusion coefficients for oxygen can be represented by D = 1.90e⁻⁵ exp (−123,382 J/RT) cm²/s and for temperatures between 100 and 300 °C the diffusion coefficients can be represented by D = 1.95e⁻¹⁰ exp (−62484 J/RT) cm²/s, where the activation energies for uraninite are 123.4 and 62.5 kJ/mol, respectively. Hydrogen diffusion in uraninite appears to be controlled by similar mechanisms as oxygen. Using the volume diffusion coefficients for temperatures between 50 and 700 °C, diffusion coefficients for hydrogen can be represented by D = 9.28e⁻⁶ exp (−156,528 J/RT) cm²/s for temperatures between 450 and 700 °C and D = 1.39e⁻¹⁴ exp (−34518 J/RT) cm²/s for temperatures between 50 and 400 °C, where the activation energies for uraninite are 156.5 and 34.5 kJ/mol, respectively.Results from these new experiments have implications for isotopic exchange during natural UO₂-water interactions. The exceptionally low δ¹⁸O values of natural uraninites (i.e. −32‰ to −19.5‰) from unconformity-type uranium deposits in Saskatchewan, in conjunction with theoretical and experimental uraninite-water and UO₃-water fractionation factors, suggest that primary uranium mineralization is not in oxygen isotopic equilibrium with coeval clay and silicate minerals. The low δ¹⁸O values have been interpreted as resulting from the low temperature overprinting of primary uranium mineralization in the presence of relatively modern meteoric fluids having δ¹⁸O values of ca. −18‰, despite petrographic and U-Pb isotope data that indicate limited alteration. Our data show that the anomalously low oxygen isotopic composition of the uraninite from the Athabasca Basin can be due to meteoric water overprinting under reducing conditions, and meteoric water or groundwater can significantly affect the oxygen isotopic composition of spent nuclear fuel in a geologic repository, with minimal change to the chemical composition or texture. Moreover, the rather fast oxygen and hydrogen diffusion coefficients for uraninite, especially at low temperatures, suggest that oxygen and hydrogen diffusion may impart characteristic isotopic signals that can be used to track the route of fissile material.     

Strontium and oxygen isotope profiles across marble-silicate contacts,Lizzies Basin,East Humboldt Range,Nevada: constraints on metamorphic permeability contrasts and fluid flow

 Sr isotope profiles across marble-silicate rock contacts are used in conjunction with previously published oxygen isotope profiles to constrain fluid movement, porosity and permeability contrasts in migmatitic rocks from Lizzies Basin in the East Humboldt Range, Nevada. The ¹⁸O/¹⁶O systematics in the high-grade sequence have been interpreted to reflect infiltration of ∼2×10² m³/m² of a relatively low ¹⁸O hydrous fluid through the sequence, but with preservation of δ¹⁸O anomalies in thin marble bands due to a 30-fold lower porosity in the marble compared with silicate rocks (Wickham and Peters 1992). The Sr isotope profiles confirm that tracer exchange between marble and silicate rock was primarily by diffusion, and in one case, indicate that porosities differed by less than a factor of four in the ∼10 cm boundary layer which exhibits diffusive modification of ⁸⁷Sr/⁸⁶Sr ratios. This contrasts with modelling of the oxygen isotope profiles which imply porosity contrasts >10 for one marble band and >50 for a second marble band. Either strontium and oxygen isotope diffusion reflect different events (possible if fluid Sr contents varied with time) or porosity varied substantially with the silicate rocks. Oxygen isotope profiles in the deeper part of the metamorphic section in which δ¹⁸O values of silicate rocks have been homogenised and lowered, indicate similar diffusion distances (and thus porosity-time evolution) to oxygen isotopic profiles higher in the section. Comparison of strontium and oxygen isotope diffusion distances constrains fluid Sr contents to between ∼50 and ∼500 ppm deep in the section, but less than ∼10 ppm higher in the section. The difference is related to release of relatively saline, Sr-rich fluids, by the abundant leucogranites and associated skarns deep in the section (cf. Peters and Wickham 1995). Received: 9 December 1994/Accepted: 13 April 1995     

Oxygen isotope exchange and disequilibrium between calcite and tremolite in the absence and presence of an experimental C–O–H fluid

Oxygen isotope exchange between minerals during metamorphism can occur in either the presence or the absence of aqueous fluids. Oxygen isotope partitioning among minerals and fluid is governed by both chemical and isotopic equilibria during these processes, which progress by intragranular and intergranular diffusion as well as by surface reactions. We have carried out isotope exchange experiments in two- and three-phase systems, respectively, between calcite and tremolite at high temperatures and pressures. The two-phase system experiments were conducted without fluid either at 1 GPa and 680 °C for 7 days or at 500 MPa and 560 °C for 20 days. Extrapolated equilibrium fractionations between calcite and tremolite are significantly lower than existing empirical estimates and experimental determinations in the presence of small amounts of fluid, but closely match calculated fractionations by means of the increment method for framework oxygen in tremolite. The small fractionations measured in the direct calcite–tremolite exchange experiments are interpreted by different rates of oxygen isotope exchange between hydroxyl oxygen, framework oxygen and calcite during the solid–solid reactions where significant recrystallization occurs. The three-phase system experiments were accomplished in the presence of a large amount of fluid (CO₂+H₂O) at 500 MPa and 560 °C under conditions of phase equilibrium for 5, 10, 20, 40, 80, 120, 160, and 200 days. The results show that oxygen isotope exchange between minerals and fluid proceeds in two stages: first, through a mechanism of dissolution-recrystallization and very rapidly; second, through a mechanism of diffusion and very slowly. Synthetic calcite shows a greater rate of isotopic exchange with fluid than natural calcite in the first stage. The rate of oxygen diffusion in calcite is approximately equal to or slightly greater than that in tremolite in the second stage. A calculation using available diffusion coefficients for calcite suggests that grain boundary diffusion, rather than volume diffusion, has been the dominant mechanism of oxygen transport between the fluid and the mineral grains in the later stage.Editorial responsibility: T.L. Grove     

Nitrogen isotopic studies in the suboxic Arabian Sea

Measurements of¹⁵N/¹⁴N in dissolved molecular nitrogen (N₂), nitrate (NO ₃ ⁻ ) and nitrous oxide (N₂O) and¹⁸O/¹⁶O in N₂O [expressed as δ¹⁵N and δ¹⁸O, relative to atmospheric N₂ and oxygen (O₂), respectively] have been made in water column at several locations in the Arabian Sea, a region with one of the thickest and most intense O₂ minima observed in the open ocean. Microbially-mediated reduction of NO ₃ ⁻ to N₂ (denitrification) in the oxygen minimum zone (OMZ) appears to greatly affect the natural isotopic abundances. The δ¹⁵N of NO ₃ ⁻ increases from 6‰ in deep waters (2500 m) to 15‰ within the core of the denitrifying layer (250–350 m); the δ¹⁵N of N₂ concurrently decreases from 0.6‰ to 0.20‰ Values of the isotopic fractionation factor (ε) during denitrification estimated using simple advection-reaction and diffusion-reaction models are 22‰ and 25‰, respectively. A strong decrease in δ¹⁵N of NO ₃ ⁻ is observed from ∼ 200m (> 11‰) to 80m (∼ 6‰); this is attributed to the input of isotopically light nitrogen through nitrogen fixation. Isotopic analysis of N₂O reveals extremely large enrichments of both¹⁵N and¹⁸O within the OMZ, presumably due to the preferential reduction of lighter N₂O to N₂. However, isotopically light N₂O is observed to accumulate in high concentrations above the OMZ indicating that the N₂O emitted to the atmosphere from this region cannot be very heavy. The isotope data from the intense upwelling zone off the southwest coast of India, where some of the highest concentrations of N₂O ever found at the sea surface are observed, show moderate depletion of¹⁵N, but slight enrichment of¹⁸O relative to air. These results suggest that the ocean-atmosphere exchange cannot counter inputs of heavier isotopes (particularly¹⁸O) associated with the stratospheric back flux, as proposed by previous workers. This calls for additional sources and/or sinks of N₂O in the atmosphere. Also, the N₂O isotope data cannot be explained by production through either nitrification or denitrification, suggesting a possible coupling between the two processes as an important mechanism of N₂O production.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

High‐resolution geochemical record of fluid–rock interaction in a mid‐crustal shear zone: a comparative study of major element and oxygen isotope transport in garnet

Garnet grains from an intensely metasomatized mid‐crustal shear zone in the Reynolds Range, central Australia, exhibit a diverse assortment of textural and compositional characteristics that provide important insights into the geochemical effects of fluid–rock interaction. Electron microprobe X‐ray maps and major element profiles, in situ secondary ion mass spectrometry oxygen isotope analyses, and U–Pb and Sm–Nd geochronology are used to reconstruct their thermal, temporal and fluid evolution. These techniques reveal a detailed sequence of garnet growth, re‐equilibration and dissolution during intracontinental reworking associated with the Ordovician–Carboniferous (450–300 Ma) Alice Springs Orogeny. A euhedral garnet porphyroblast displays bell‐shaped major element profiles diagnostic of prograde growth zoning during shear zone burial. Coexisting granulitic garnet porphyroclasts inherited from precursor wall rocks show extensive cation re‐equilibration assisted by fracturing and fragmentation. Oxygen isotope variations in the former are inversely correlated with the molar proportion of grossular, suggesting that isotopic fractionation is linked to Ca substitution. The latter generally show close correspondence to the isotopic composition of their precursor, indicating slow intergranular diffusion of O relative to Fe²⁺, Mg and Mn. Peak metamorphism associated with shearing (～550 °C; 5.0–6.5 kbar) occurred at c. 360 Ma, followed by rapid exhumation and cooling. Progressive Mn enrichment in rim domains indicates that the retrograde evolution caused partial garnet dissolution. Accompanying intra‐mineral porosity production then stimulated limited oxygen isotope exchange between relict granulitic garnet grains and adjacent metasomatic biotite, resulting in increased garnet δ¹⁸O values over length scales <200 μm. Spatially restricted oxygen interdiffusion was thus facilitated by increased fluid access to reaction interfaces. The concentration of Ca in channelled fracture networks suggests that its mobility was enhanced by a similar mechanism. In contrast, the intergranular diffusion of Fe²⁺, Mg and Mn was rock‐wide under the same P–T regime, as demonstrated by a lack of local spatial variations in the re‐equilibration of these components. The extraction of detailed reaction histories from garnet must therefore take into account the variable length‐ and time‐scales of elemental and isotopic exchange, particularly where the involvement of a fluid phase enhances the possibility of measureable resetting profiles being generated for slowly diffusing components such as Ca and O, even at low ambient temperatures and relatively fast cooling rates.     

Imprint of meteoric water on the stable isotope compositions of igneous and secondary minerals,Kap Edvard Holm Complex,East Greenland

 Hydrogen and oxygen isotope analyses have been made of hydrous minerals in gabbros and basaltic xenoliths from the Eocene Kap Edvard Holm intrusive complex of East Greenland. The analyzed samples are of three types: (1) primary igneous hornblendes and phlogopites that crystallized from partial melts of hydrothermally altered basaltic xenoliths, (2) primary igneous hornblendes that formed during late–magmatic recrystallization of layered gabbroic cumulates, and (3) secondary actinolite, epidote and chlorite that formed during subsolidus alteration of both xenoliths and gabbros. Secondary actinolite has a δ¹⁸O value of −5.8‰ and a δD value of −158‰. These low values reflect subsolidus alteration by low–δ¹⁸O, low–δD hydrothermal fluids of meteoric origin. The δD value is lower than the −146 to −112‰ values previously reported for amphiboles from other early Tertiary meteoric–hydrothermal systems in East Greenland and Scotland, indicating that the meteoric waters at Kap Edvard Holm were isotopically lighter than typical early Tertiary meteoric waters in the North Atlantic region. This probably reflects local climatic variations caused by formation of a major topographic dome at about the time of plutonism and hydrothermal activity. The calculated isotopic composition of the meteoric water is δD=−110 ± 10‰, δ¹⁸O ≈−15‰. Igneous hornblendes and phlogopites from pegmatitic pods in hornfelsed basaltic xenoliths have δ¹⁸O values between −6.0 and −3.8‰ and δD values between −155 and −140‰. These are both much lower than typical values of fresh basalts. The oxygen isotope fractionations between pegmatitic hornblendes and surrounding hornfelsic minerals are close to equilibrium fractionations for magmatic temperatures, indicating that the pegmatites crystallized from low–δ¹⁸O partial melts of xenoliths that had been hydrothermally altered and depleted in ¹⁸O prior to stoping. The pegmatitic minerals may have crystallized with low primary δD values inherited from the altered country rocks, but these values were probably overprinted extensively by subsolidus isotopic exchange with low–δD meteoric–hydrothermal fluids. This exchange was facilitated by rapid self–diffusion of hydrogen through the crystal structures. Primary igneous hornblendes from the plutonic rocks have δ¹⁸O values between +2.0 and +3.2‰ and δD values between −166 and −146‰. The ¹⁸O fractionations between hornblendes and coexisting augites are close to equilibrium fractionations for magmatic temperatures, indicating that the hornblendes crystallized directly from the magma and subsequently underwent little or no oxygen exchange. The hornblendes may have crystallized with low primary δD values, due to contamination of the magma with altered xenolithic material, but the final δD values were probably controlled largely by subsolidus isotopic exchange. This inference is based partly on the observation that coexisting plagioclase has been extensively depleted in ¹⁸O via a mineral–fluid exchange reaction that is much slower than the hydrogen exchange reaction in hornblende. It is concluded that all hydrous minerals in the study area, whether igneous or secondary, have δD values that reflect extensive subsolidus isotopic equilibration with meteoric–hydrothermal fluids. Received: 22 March 1994 / Accepted: 26 January 1995     

Modelling δC and δO in the solution layer on stalagmite surfaces

We derive equations describing the evolution of the carbon and oxygen isotope composition of the bicarbonate in a calcite precipitating solution on the surface of a stalagmite using a classical Rayleigh approach. The combined effects of calcite precipitation, degassing of CO₂ and the buffering effect of the water reservoir are taken into account. Whereas δ¹³C shows a progressive increase to a final constant value, δ¹⁸O shows an initial isotopic enrichment, which exponentially decays due to the buffering effect of the water reservoir. The calculated evolution is significantly different for both carbon and oxygen isotopes than derived in a recent paper [Dreybrodt W. (2008) Evolution of the isotopic composition of carbon and oxygen in a calcite precipitating H₂O-CO₂-CaCO₃ solution and the related isotopic composition of calcite in stalagmites. Geochim. Cosmochim. Acta72, 4712-4724.].Furthermore, we discuss the isotopic evolution of the bicarbonate in the solution for long residence times on the stalagmite surface, i.e., for t→∞. The equilibrium isotope ratio of the bicarbonate is then determined by isotopic exchange between the cave atmosphere and the bicarbonate in the solution and can be calculated by equilibrium isotope fractionation. For strongly ventilated caves exchange with the cave atmosphere will result in higher δ¹³C and δ¹⁸O values than those observed in a pure Rayleigh distillation scenario, for sparsely ventilated caves it will result in lower δ¹³C and δ¹⁸O values.     

Oxygen isotope thermometry using quartz inclusions in garnet

Oxygen isotope ratios of quartz inclusions (QI) within garnet from granulite and amphibolite facies gneisses in the Adirondack Mountains, NY were analysed and used to determine metamorphic temperatures. Primary QI for eight of 12 samples have δ¹⁸O values significantly lower than matrix quartz (MQ). The primary QI retain δ¹⁸O values representative of thermal conditions during garnet crystallization, whereas the δ¹⁸O values of MQ were raised by diffusive exchange with other matrix minerals (e.g. mica and feldspar) during cooling. The δ¹⁸O differences between QI and MQ show that garnet (a mineral with slow diffusion of oxygen) can armour QI from isotopic exchange with surrounding matrix, even during slow cooling. These differences between δ¹⁸O in MQ and QI can further be used to test cooling rates by Fast Grain Boundary diffusion modelling. Criteria for identifying QI that preserve primary compositions and are suitable for thermometry were developed based on comparative tests. Relations between δ¹⁸O and inclusion size, distance of inclusion to host–garnet rim, core–rim zonation of individual inclusions, and presence or absence of petrological features (healed cracks in QI, inclusions in contact with garnet cracks lined by secondary minerals, and secondary minerals along the inclusion grain boundary) were investigated. In this study, 61% of QI preserve primary δ¹⁸O and 39% were associated with features that were linked to reset δ¹⁸O values. If δ¹⁸O in garnet is homogeneous and inclusions are removed, laser‐fluorination δ¹⁸O values of bulk garnet are more precise, more accurate, and best for thermometry. Intragrain δ¹⁸O(Grt) profiles measured in situ by ion microprobe show no δ¹⁸O zonation. Almandine–rich garnet (Alm_60–75) from each sample was measured by laser‐fluorination mass‐spectrometry (LF‐MS) for δ¹⁸O and compared with ion microprobe measurements of δ¹⁸O in QI for thermometry. The Δ¹⁸O(Qz–Grt) values for Adirondack samples range from 2.66 to 3.24‰, corresponding to temperatures of 640–740 °C (A[Qz–Alm] = 2.71). Out of 12 samples that were used for thermometry, nine are consistent with previous estimates of peak temperature (625–800 °C) based on petrological and carbon–isotope thermometry for regional granulite and upper amphibolite facies metamorphism. The three samples that disagree with independent thermometry for peak metamorphism are from the anorthosite–mangerite–charnockite–granite suite in the central Adirondacks and yield temperatures of 640–665 °C, ~100 °C lower than previous estimates. These low temperatures could be interpreted as thermal conditions during late (post‐peak) crystallization of garnet on the retrograde path.     

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Understanding the relationship between stable isotope signals recorded in speleothems (δ¹³C and δ¹⁸O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO₂.The water entering the cave flows as a thin film towards the drip site. CO₂ degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ¹³C value of the drip water is mainly determined by the isotopic composition of soil CO₂. The evolution of the δ¹⁸O value of the carbonate species is determined by the long exchange time T_ex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO₂ in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ¹⁸O value of the carbonate species. Consequently, the δ¹⁸O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO₂-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τ_p, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since T_ex ? τ_p, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals T_d < 0.1τ_p the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.