Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

A general algorithm for the O abundance correction to C/C determinations from CO2 isotopologue measurements, including CO2 characterised by ‘mass-independent’ oxygen isotope distributions

It is widely recognised that a significant limitation to the ultimate precision of carbon stable isotope ratio measurements, as obtained from dual-inlet mass spectrometric measurements of CO₂ isotopologue ion abundances at m/z 44, 45, and 46, is the correction for interference from ¹⁷O-bearing molecular ions. Two long-established, alternative procedures for determining the magnitude of this correction are in widespread use (although only one has IAEA approval); their differences lead to small but potentially significant discrepancies in the magnitude of the resulting correction. Furthermore, neither approach was designed to accommodate oxygen three-isotope distributions which do not conform to terrestrial mass-dependent behaviour. Stratospheric CO₂, for example, contains a strongly ‘mass-independent’ oxygen isotope composition. A new strategy for determining the ¹⁷O-bearing ion correction is presented, for application where the oxygen three-isotope characteristics of the analyte CO₂ are accurately known (or assigned) in terms of the slope λ of the three-isotope fractionation line and the ordinate axis intercept 10³ ln(1 + k) on a 10³ ln(1 + δ¹⁷O) versus 10³ ln(1 + δ¹⁸O) plot. At the heart of the approach is the relationship between ¹⁷R, which is the ¹⁷O/¹⁶O ratio of the sample CO₂, and other assigned or empirically determined parameters needed for the δ¹³C evaluation:

     

Reformulated O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios

Mass-spectrometric stable isotope measurements of CO₂ use molecular ion currents at mass-to-charge ratios m/z 44, 45 and 46 to derive the elemental isotope ratios n(¹³C)/n(¹²C) and n(¹⁸O)/n(¹⁶O), abbreviated ¹³C/¹²C and ¹⁸O/¹⁶O, relative to a reference. The ion currents have to be corrected for the contribution of ¹⁷O-bearing isotopologues, the so-called ‘¹⁷O correction’. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing ¹³C/¹²C (¹³R), ¹⁷O/¹⁶O (¹⁷R) and ¹⁸O/¹⁶O (¹⁸R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO₂ generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H₃PO₄ at 25 °C (VPDB-CO₂). I find , ¹⁸R_VSMOW/10⁻⁶ = 2005.20 ± 0.45, ¹³R_VPDB-CO2/10^-6= 11124 ± 45, and ¹⁸R_VPDB-CO2/10^-6=2088.37±0.90. I also rephrase the calculation scheme for the ¹⁷O correction completely in terms of relative isotope ratio differences (δ values). This reveals that only ratios of isotope ratios (namely, ¹⁷R/¹³R and ¹³R¹⁷R/¹⁸R) are required for the ¹⁷O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative ¹³C/¹²C difference, but not for¹⁸O/¹⁶O. Even though inter-laboratory differences can be corrected for by a common ‘ratio assumption set’ and/or normalisation, the ultimate accuracy of the ¹⁷O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between ¹⁷O/¹⁶O and ¹⁸O/¹⁶O isotope ratios. For highest accuracy in the ¹³C/¹²C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that allows direct measurement of ¹³R¹⁷R/¹⁸R.     

The isotopic ratios O/O and O/O in molecular oxygen and their significance in biogeochemistry

Recently, a new method has been introduced for the estimation of photosynthetic oxygen production from the triple isotope composition (δ¹⁷O and δ¹⁸O) of dissolved O₂ in the ocean and of air O₂ in ice cores. This method is based on the deviations (¹⁷Δ) from mass dependent respiratory fractionation, the major process affecting the isotopic composition of air O₂. To apply this method, the slope in the ¹⁷O/¹⁶O vs. ¹⁸O/¹⁶O relationship used for ¹⁷Δ calculation must be known with high accuracy. Using numerical simulations and closed system experiments, we show how the respiratory slope is manifested in the ¹⁷Δ of O₂ in situations where respiration is the only process affecting oxygen isotopic composition (kinetic slope), and in systems in steady state between photosynthesis and respiration (steady state slope). The slopes of the fractionation line in these two cases are different, and the reasons of this phenomenon are discussed. To determine the kinetic respiratory slope for the dominant O₂ consumers in aquatic systems, we have conducted new experiments using a wide range of organisms and conditions and obtained one universal value (0.5179 ± 0.0006) in ln(δ¹⁷O + 1) vs. ln(δ¹⁸O + 1) plots. It was also shown that the respiratory fractionations under light and dark are identical within experimental error. We discuss various marine situations and conclude that the kinetic slope 0.518 should be used for calculating ¹⁷Δ of dissolved O₂. In contrast, a steady state fractionation slope should be used in global mass balance calculations of triple isotope ratios of O₂ in air records of ice cores.     

Experimental and numerical studies of the O exchange between CO2 and water in the atmosphere-soil invasion flux

The ¹⁸O/¹⁶O ratio of CO₂ is a potentially powerful tracer of carbon dioxide fluxes from the soil to the atmosphere, which is influenced by complex interactions involving both biotic and abiotic soil processes. We use a simplified experimental approach and numerical simulations to examine in isolation the ¹⁸O exchange between CO₂ and soil water associated with the abiotic invasion of atmospheric CO₂ into soil. This allowed us to verify, in particular, whether the ¹⁸O of the retro-diffusion flux of CO₂ from the soil reflects ¹⁸O equilibration with water at the soil surface, or at some depth. Sterile soil samples with known water isotopic composition were placed in a closed box attached to a specially designed flow chamber and the changes in δ¹⁸O of CO₂ between the chamber inlet and outlet, due only to invasion effects, were determined. Numerical simulations constrained by the laboratory gas exchange measurements indicated that between the two commonly used diffusion models [Penman, H.L. (1940). Gas and vapor movements in soil, 1: the diffusion of vapors through porous solids. Int. J. Agric. Sci.30, 437-462; Moldrup, P., Olesen, T., Yamaguchi, T., Schjonning, P., Rolston, D.E. (1999). Modeling diffusion and reaction in soils, IX, the Backingham-Burdine-Campbell equation for gas diffusivity in undisturbed soil. Soil Sci.164, 542-551], only the former provided good agreement with the measurements over a wide range of soil water contents. Based on the model calculations constrained by experimental data, and on comparison of characteristic diffusion/reaction times, we conclude that the depth required for full CO₂-water ¹⁸O equilibration ranges between 2 and 8.5 cm. The depth depends, in order of importance, on (1) soil moisture content; (2) temperature, which dominates the rate of hydration isotopic exchange; (3) CO₂ residence time, which is determined by the time of replacement of the column air above the soil; and (4) soil structure, including porosity, tortuosity and grain size, with the later probably influencing the water surface area exposed to CO₂ exchange. Using field data from a semi-arid forest site in Israel, numerical simulations indicated that the ¹⁸O full equilibrium depth varied at this site between 4 cm (January) and 8 cm (November), being sensitive mostly to temperature and soil water content. Deepening of the equilibration depth as the soil dries should limit the effects of ¹⁸O evaporative enrichment at the surface on the isotopic composition of the soil-atmosphere CO₂ flux.     

Fractionation of oxygen and hydrogen isotopes in evaporating water

Variations in oxygen and hydrogen isotope ratios of water and ice are powerful tools in hydrology and ice core studies. These variations are controlled by both equilibrium and kinetic isotope effects during evaporation and precipitation, and for quantitative interpretation it is necessary to understand how these processes affect the isotopic composition of water and ice. Whereas the equilibrium isotope effects are reasonably well understood, there is controversy on the magnitude of the kinetic isotope effects of both oxygen and hydrogen and the ratio between them. In order to resolve this disagreement, we performed evaporation experiments into air, argon and helium over the temperature range from 10 to 70 °C. From these measurements we derived the isotope effects for vapor diffusion in gas phase (ε_{diff(HD¹⁶O)} for D/H and ε_{diff(H2¹⁸O)} for ¹⁸O/¹⁶O). For air, the ratio ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} at 20 °C is 0.84, in very good agreement with Merlivat (1978) (0.88), but in considerable inconsistency with Cappa et al. (2003) (0.52). Our results support Merlivat’s conclusion that measured ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} ratios are significantly different than ratios calculated from simplified kinetic theory of gas diffusion. On the other hand, our experiments with helium and argon suggest that this discrepancy is not due to isotope effects of molecular collision diameters. We also found, for the first time, that the ε_{diff(HD¹⁶O)}/ε_{diff(H2¹⁸O)} ratio tends to increase with cooling. This new finding may have important implications to interpretations of deuterium excess (d-excess = δD − 8δ¹⁸O) in ice core records, because as we show, the effect of temperature on d-excess is of similar magnitude to glacial interglacial variations in the cores.     

Abundance of mass 47 CO2 in urban air, car exhaust, and human breath

Atmospheric carbon dioxide is widely studied using records of CO₂ mixing ratio, δ¹³C and δ¹⁸O. However, the number and variability of sources and sinks prevents these alone from uniquely defining the budget. Carbon dioxide having a mass of 47 u (principally ¹³C¹⁸O¹⁶O) provides an additional constraint. In particular, the mass 47 anomaly (Δ₄₇) can distinguish between CO₂ produced by high temperature combustion processes vs. low temperature respiratory processes. Δ₄₇ is defined as the abundance of mass 47 isotopologues in excess of that expected for a random distribution of isotopes, where random distribution means that the abundance of an isotopologue is the product of abundances of the isotopes it is composed of and is calculated based on the measured ¹³C and ¹⁸O values. In this study, we estimate the δ¹³C (vs. VPDB), δ¹⁸O (vs. VSMOW), δ47, and Δ₄₇ values of CO₂ from car exhaust and from human breath, by constructing ‘Keeling plots’ using samples that are mixtures of ambient air and CO₂ from these sources. δ47 is defined as , where is the R⁴⁷ value for a hypothetical CO₂ whose δ¹³C_VPDB = 0, δ¹⁸O_VSMOW = 0, and Δ₄₇ = 0. Ambient air in Pasadena, CA, where this study was conducted, varied in [CO₂] from 383 to 404 μmol mol⁻¹, in δ¹³C and δ¹⁸O from −9.2 to −10.2‰ and from 40.6 to 41.9‰, respectively, in δ47 from 32.5 to 33.9‰, and in Δ₄₇ from 0.73 to 0.96‰. Air sampled at varying distances from a car exhaust pipe was enriched in a combustion source having a composition, as determined by a ‘Keeling plot’ intercept, of −24.4 ± 0.2‰ for δ¹³C (similar to the δ¹³C of local gasoline), δ¹⁸O of 29.9 ± 0.4‰, δ47 of 6.6 ± 0.6‰, and Δ₄₇ of 0.41 ± 0.03‰. Both δ¹⁸O and Δ₄₇ values of the car exhaust end-member are consistent with that expected for thermodynamic equilibrium at∼200 °C between CO₂ and water generated by combustion of gasoline-air mixtures. Samples of CO₂ from human breath were found to have δ¹³C and δ¹⁸O values broadly similar to those of car exhaust-air mixtures, −22.3 ± 0.2 and 34.3 ± 0.3‰, respectively, and δ47 of 13.4 ± 0.4‰. Δ₄₇ in human breath was 0.76  ± 0.03‰, similar to that of ambient Pasadena air and higher than that of the car exhaust signature.     

The triple isotopic composition of oxygen in leaf water

The isotopic composition of atmospheric O₂ depends on the rates of oxygen cycling in photosynthesis, respiration, photochemical reactions in the stratosphere and on δ¹⁷O and δ¹⁸O of ocean and leaf water. While most of the factors affecting δ¹⁷O and δ¹⁸O of air O₂ have been studied extensively in recent years, δ¹⁷O of leaf water—the substrate for all terrestrial photosynthesis—remained unknown. In order to understand the isotopic composition of atmospheric O₂ at present and in fossil air in ice cores, we studied leaf water in field experiments in Israel and in a European survey. We measured the difference in δ¹⁷O and δ¹⁸O between stem and leaf water, which is the result of isotope enrichment during transpiration. We calculated the slopes of the lines linking the isotopic compositions of stem and leaf water. The obtained slopes in ln(δ¹⁷O + 1) vs. ln(δ¹⁸O + 1) plots are characterized by very high precision (∼0.001) despite of relatively large differences between duplicates in both δ¹⁷O and δ¹⁸O (0.02-0.05‰). This is so because the errors in δ¹⁸O and δ¹⁷O are mass-dependent. The slope of the leaf transpiration process varied between 0.5111 ± 0.0013 and 0.5204 ± 0.0005, which is considerably smaller than the slope linking liquid water and vapor at equilibrium (0.529). We further found that the slope of the transpiration process decreases with atmospheric relative humidity (h) as 0.522-0.008 × h, for h in the range 0.3-1. This slope is neither influenced by the plant species, nor by the environmental conditions where plants grow nor does it show strong variations along long leaves.     

The non-mass-dependent oxygen isotope effect in the electrodissociation of carbon dioxide: A step toward understanding NoMaD chemistry

A non-mass dependent (NoMaD) oxygen isotope effect is demonstrated in the dissociation of CO₂ similar to that observed in the electrosynthesis of ozone. The molecular oxygen produced carries the signature of two separate isotopic fractionation processes; a mass-dependent fractionation probably due to CO₂ + O isotopic exchange, and a secondary NoMaD fractionation (δ¹⁷O = 0.97 ± 0.09δ¹⁸O, with the O₂ depleted in ¹⁷O and ¹⁸O). It is suggested that the effect is due to either the formation or relaxation of ozone in an excited electronic state. This represents the latest advance in the understanding of chemical NoMaD effects which may be essential to the explanation of non-mass-dependent fractionations observed in meteorites.     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.     

N/N and O/O stable isotope ratios of nitrous oxide produced during denitrification in temperate forest soils

Anaerobic incubations of upland and wetland temperate forest soils from the same watershed were conducted under different moisture and temperature conditions. Rates of nitrous oxide (N₂O) production by denitrification of nitrate () and the stable isotopic composition of the N₂O (δ¹⁵N, δ¹⁸O) were measured. In all soils, N₂O production increased with elevated temperature and soil moisture. At each temperature and moisture level, the rate of N₂O production in the wetland soil was greater than in the upland soil. The ¹⁵N isotope effect (ε) _{(product − substrate)} ranged from −20‰ to −29‰. These results are consistent with other published estimates of ¹⁵N fractionation from both single species culture experiments and soil incubation studies from different ecosystems.A series of incubations were conducted with ¹⁸O-enriched water (H₂O) to determine if significant oxygen exchange (O-exchange) occurred between H₂O and N₂O precursors during denitrification. The exchange of H₂O-O with nitrite () and/or nitric oxide (NO) oxygen has been documented in single organism culture studies but has not been demonstrated in soils prior to this study. The fraction of N₂O-O derived from H₂O-O was confined to a strikingly narrow range that differed between soil types. H₂O-O incorporation into N₂O produced from upland and wetland soils was 86% to 94% and 64% to 70%, respectively. Neither the temperature, soil moisture, nor the rate of N₂O production influenced the magnitude of O-exchange. With the exception of one treatment, the net ¹⁸O isotope effect (ε_net) _{(product-substrate)} ranged from +37‰ to +43‰.Most previous studies that have reported ¹⁸O isotope effects for denitrification of to N₂O have failed to account for the effect of oxygen exchange with H₂O. When high amounts of O-exchange occur after fractionation during reductive O-loss, the ¹⁸O-enrichment is effectively lost or diminished and δ¹⁸O-N₂O values will be largely dictated by δ¹⁸O-H₂O values and subsequent fractionation. The process and extent of O-exchange, combined with the magnitude of oxygen isotope fractionation at each reduction step, appear to be the dominant controls on the observed oxygen isotope effect. In these experiments, significant oxygen isotope fractionation was observed to occur after the majority of water O-exchange. Due to the importance of O-exchange, the net oxygen isotope effect for N₂O production in soils can only be determined using δ¹⁸O-H₂O addition experiments with δ¹⁸O-H₂O close to natural abundance.The results of this study support the continued use of δ¹⁵N-N₂O analysis to fingerprint N₂O produced from the denitrification of . The utilization of ¹⁸O/¹⁶O ratios of N₂O to study N₂O production pathways in soil environments is complicated by oxygen exchange with water, which is not usually quantified in field studies. The oxygen isotope fractionation observed in this study was confined to a narrow range, and there was a clear difference in water O-exchange between soil types regardless of temperature, soil moisture, and N₂O production rate. This suggests that ¹⁸O/¹⁶O ratios of N₂O may be useful in characterizing the actively denitrifying microbial community.     

A model for O/O variations in CO2 evolved from goethite during the solid-state α-FeOOH to α-Fe2O3 phase transition

“Plateau” δ¹⁸O values of CO₂ that evolved from the Fe(CO₃)OH component during isothermal vacuum dehydrations (200-230 °C) of 18 natural goethites range from 8.2 to 28.1‰. In contrast, the measured δ¹⁸O values of the goethite structural oxygen range from −11.3 to 1.7‰. The results of this study indicate that the apparent oxygen isotope fractionation factor (¹⁸α_app) between plateau CO₂ and initial goethite is systematically related to the rate of isothermal vacuum dehydration. The nonlinear correlation and the magnitudes of the ¹⁸α_app values are predicted by a relatively simple mass balance model with the following assumptions: (1) the rate of isothermal vacuum dehydration of goethite (for the interval from 0 to ∼60 to 80% loss of structural hydroxyl hydrogen) can be reasonably well represented by first-order kinetics and (2) isotopic exchange between evolving H₂O vapor and solid occurs only in successive, local transition states. The generally good correspondence between the model predictions and the experimental data seems to validate these assumptions. Thus, the ¹⁸O/¹⁶O ratios of the evolved CO₂ can act as probes into the transient processes operating at the molecular level during the solid-state goethite-to-hematite phase transition. For example, the activation energy for the rate constant associated with the transition state, oxygen isotopic exchange between solid and H₂O vapor, is tentatively estimated as 28 ± 11 KJ/mol. Such knowledge may be of consequence in understanding the significance of ¹⁸O/¹⁶O ratios in hematites from some natural environments (e.g., Mars?).Kinetic data and δ¹⁸O values of CO₂ are routinely obtained in the course of measurements of the abundance and δ¹³C values of the Fe(CO₃)OH in goethite. The observed correlation between ¹⁸α_app and dehydration rates suggests that plateau δ¹⁸O values of evolved CO₂ may provide complementary estimates of the δ¹⁸O values of total goethite structural oxygen (O, OH, CO₂) with an overall precision of about ±1‰. However, because of isotopic exchange during the dehydration process, δ¹⁸O values of the evolved CO₂ do not reflect the original δ¹⁸O values of the CO₂ that was occluded as Fe(CO₃)OH in goethite.     

Stable isotope composition of CO2 outgassed from cores of argillites: a simple method to constrain δ18O of porewater and δ13C of dissolved carbon in mudrocks

Stable isotope characterization of porewater, and dissolved species, in mudrocks and argillaceous rocks is notoriously difficult. Techniques based on physical or chemical extraction of porewater can generate significant analytical artefacts. The authors report a novel, simple approach to determine the δ¹⁸O of porewater and δ¹³C of dissolved C in argillites. The method uses core samples placed in specifically-designed outgassing cells, sealed shortly after drilling and stored in well-controlled conditions. After 1–2 months, CO₂ naturally outgassed by argillite porewater is collected, purified and analyzed for C and O isotopes. Porewater δ¹⁸O and dissolved C δ¹³C are calculated from CO₂ isotope data using appropriate fractionation factors. This methodology was successfully applied to the Callovo-Oxfordian argillites from Bure (eastern Paris Basin, France) and the Opalinus Clay formation from Mont Terri (Switzerland). In both clay formations, results indicate that porewater is meteoric and dissolved C is of marine origin. The main advantage of the approach is that it does not induce any major physical or chemical disturbance to the clay–water system investigated. Further testing on argillaceous rocks of variable composition and organic content is needed to assess extent of applicability.     

Modelling fractionation of stable isotopes in stalagmites

High resolution δ¹³C and δ¹⁸O profiles recorded in precisely dated speleothems are widely used proxies for the climate of the past. Both δ¹³C and δ¹⁸O depend on several climate related effects including meteorological processes, processes occurring in the soil zone above the cave and isotope fractionation processes occurring in the solution layer on the stalagmite surface. Here we model the latter using a stalagmite isotope and growth model and determine the relationship between the stable isotope values in speleothem calcite and cave parameters, such as temperature, drip interval, water p_CO2 and a mixing coefficient describing mixing processes between the solution layer and the impinging drop.The evolution of δ¹³C values is modelled as a Rayleigh distillation process and shows a pronounced dependence on the residence time of the solution on the stalagmite surface and the drip interval, respectively. The evolution of δ¹⁸O values, in contrast, is also influenced by buffering reactions between the bicarbonate in the solution and the drip water driving the δ¹⁸O value of the bicarbonate towards the value expected for equilibrium isotope fractionation between drip water and calcite. This attenuates the dependence of the δ¹⁸O values on drip interval. The temperature dependence of δ¹⁸O, however, is more pronounced than for δ¹³C and in a similar range as expected for fractionation under equilibrium conditions.We also investigate the isotopic enrichment of the δ¹³C and δ¹⁸O values along individual growth layers and, thus, the slopes expected for Hendy tests. The results show that a positive Hendy test is only possible if isotope fractionation occurred under disequilibrium conditions. However, a negative Hendy test does not exclude that isotope fractionation occurred under disequilibrium conditions. A more reliable indicator for disequilibrium fractionation is the enrichment of the δ¹³C values along an individual growth layer.     

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.     

Mass-independent fractionation of oxygen isotopes in the mesostasis of a chondrule from the Semarkona LL3.0 ordinary chondrite

A large chondrule from Semarkona, the most primitive ordinary chondrite known, has been discovered to contain a record of mass transport during its formation. In most respects, it is a normal Type I, group A1, low-FeO chondrule that was produced by reduction and mass-loss during the unidentified flash-heating event that produced the chondrules, the most abundant structural component in primitive meteorites. We have previously measured elemental abundances and abundance profiles in this chondrule. We here report oxygen isotope ratio abundances and ratio abundance profiles. We have found that the mesostasis is zoned in oxygen isotope ratio, with the center of the chondrule containing isotopically heavier oxygen than the outer regions, the outer regions being volatile rich from the diffusion of volatiles into the chondrule during cooling. The δ¹⁷O values range from −2.0‰ to 9.9‰, while δ¹⁸O range from −1.9‰ to 9.6‰. More importantly, a plot of δ¹⁷O against δ¹⁸O has a slope of 1.1 ± 0.2 (1σ) and 0.88 ± 0.10 (1σ) when measured by two independent methods. Co-variation of δ¹⁷O with δ¹⁸O that does not follow mass-dependent fractionation has often been seen in primitive solar system materials and is usually ascribed to the mixing of different oxygen reservoirs. We argue that petrographic and compositional data indicate that this chondrule was completely melted at the time of its formation so that relic grains could not have survived. Furthermore, there is petrographic and compositional evidence that there was no aqueous alteration of this chondrule subsequent to its formation. Although it is possible to formulate a series of exchanges between the chondrule and external ¹⁶O-rich and ¹⁶O-poor reservoirs that may explain the detailed oxygen isotope systematics of this chondrule, such a sequence of events looks very contrived. We therefore hypothesize that reduction, devolatilization, and crystallization of the chondrule melt may have produced ¹⁶O-rich olivines and ¹⁶O-poor mesostasis plotting on a slope-one line as part of the chondrule-forming process in an analogous fashion to known chemical mass-independent isotopic fractionation mechanisms. During cooling, volatiles and oxygen near the terrestrial line in oxygen isotope composition produced the outer zone of volatile rich and ¹⁶O-rich mesostasis. The chondrule therefore not only retains a record of considerable mass transport accompanying formation, but also may indicate that the isotopes of oxygen underwent mass-independent fractionation during the process.     

Reconstruction of seasonal temperature variability in the tropical Pacific Ocean from the shell of the scallop, Comptopallium radula

We investigated the oxygen isotope composition (δ¹⁸O) of shell striae from juvenile Comptopallium radula (Mollusca; Pectinidae) specimens collected live in New Caledonia. Bottom-water temperature and salinity were monitored in-situ throughout the study period. External shell striae form with a 2-day periodicity in this scallop, making it possible to estimate the date of precipitation for each calcite sample collected along a growth transect. The oxygen isotope composition of shell calcite (δ¹⁸O_{shell calcite}) measured at almost weekly resolution on calcite accreted between August 2002 and July 2003 accurately tracks bottom-water temperatures. A new empirical paleotemperature equation for this scallop species relates temperature and δ¹⁸O_{shell calcite}:

t(°C)=20.00(±0.61)-3.66(±0.39)×(δ¹⁸O_{shell calcite VPDB}-δ¹⁸O_{water VSMOW})     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

Rhinocerotid tooth enamel 18O/16O variability between 23 and 12 Ma in southwestern France

The relationship between the oxygen isotope ratio of mammal tooth enamel and that of drinking water was used to reconstruct changes in the Miocene oxygen isotope ratio of rainfall (meteoric water ${\delta }^{18}$O_MW). These, in turn, are related to climatic parameters (temperature, precipitation and evaporation rate). ${\delta }^{18}$O values of rhinocerotid teeth from the Aquitaine Basin (southwestern France) suggest a significant climatic change between 17 and 12 Ma, characterized by cooling together with precipitation increase, in agreement with other terrestrial and oceanic records. To cite this article: I. Bentaleb et al., C. R. Geoscience 338 (2006).     

O/O and D/H ratios of pedogenic kaolinite in a North American Cenomanian laterite: Paleoclimatic implications

Kaolinite, gibbsite and quartz are the dominant minerals in samples collected from two outcrops of a Cenomanian (∼95 Ma) laterite in southwestern Minnesota. A combination of measured yields and isotope ratios permitted mass balance calculations of the δD and δ¹⁸O values of the kaolinite in these samples. These calculations yielded kaolinite δD values of about −73‰ and δ¹⁸O values of about +18.7‰. The δD and δ¹⁸O values appear to preserve information on the ancient weathering system.If formed in hydrogen and oxygen isotope equilibrium with water characterized by the global meteoric water line (GMWL), the kaolinite δD and δ¹⁸O values indicate a crystallization temperature of 22 (±5) °C. A nominal paleotemperature of 22 °C implies a δ¹⁸O value for the corresponding water of −6.3‰. The combination of temperature and meteoric water δ¹⁸O values is consistent with relatively intense rainfall at that mid-paleolatitude location (∼40°N) on the eastern shore of the North American Western Interior Seaway. The inferred Cenomanian paleosol temperature of ∼22 °C is in general accord with published mid-Cretaceous continental mean annual temperatures (MAT) estimated from leaf margin analyses of fossil plants.When compared with results from a published GCM-based Cenomanian climate simulation which specifies a latitudinal sea surface temperature (SST) gradient that was either near modern or smaller-than-modern, the kaolinite paleotemperature of 22 °C is closer to the GCM-predicted MAT for a smaller equator-to-pole temperature difference in the mid-Cretaceous. Moreover, the warm, kaolinite-derived, mid-paleolatitude temperature of 22 °C is associated with proxy estimates of high concentrations of atmospheric CO₂ in the Cenomanian. The overall similarity of proxy and model results suggests that the general features of Cenomanian continental climate in that North American locale are probably being revealed.