OCO in Earth’s atmosphere

The chemistry and budgets of atmospheric gases are constrained by their bulk stable isotope compositions (e.g., δ¹³C values), which are based on mixing ratios of isotopologues containing one rare isotope (e.g., ¹⁶O¹³C¹⁶O). Atmospheric gases also have isotopologues containing two or more rare isotopes (e.g., ¹⁸O¹³C¹⁶O). These species have unique physical and chemical properties and could help constrain origins of atmospheric gases and expand the scope of stable isotope geochemistry generally. We present the first measurements of the abundance of ¹⁸O¹³C¹⁶O from natural and synthetic sources, discuss the factors influencing its natural distribution and, as an example of its applied use, demonstrate how its abundance constrains the sources of CO₂ in the Los Angeles basin. The concentration of ¹⁸O¹³C¹⁶O in air can be explained as a combination of ca. 1‰ enrichment (relative to the abundance expected if C and O isotopes are randomly distributed among all possible isotopologues) due to enhanced thermodynamic stability of this isotopologue during isotopic exchange with leaf and surface waters, ca. 0.1‰ depletion due to diffusion through leaf stomata, and subtle (ca. 0.05‰) dilution by ¹⁸O¹³C¹⁶O-poor anthropogenic CO₂. Some air samples are slightly (ca. 0.05‰) lower in ¹⁸O¹³C¹⁶O than can be explained by these factors alone. Our results suggest that ¹⁸O¹³C¹⁶O abundances should vary by up to ca. 0.2‰ with latitude and season, and might have measurable sensitivities to stomatal conductances of land plants. We suggest the greatest use of Δ₄₇ measurements will be to “leverage” interpretation of the δ¹⁸O of atmospheric CO₂.     

An approach to estimate Lower Jurassic seawater oxygen‐isotope composition using δ18O and Mg/Ca ratios of belemnite calcites (Early Pliensbachian,northern Spain)

Palaeotemperature estimates from the oxygen‐isotope compositions of belemnites have been hampered by not knowing ancient seawater isotope compositions well enough. We have tackled this problem using Mg/Ca as a proxy for temperature and here, we present a ~2 Ma record of paired Mg/Ca and δ¹⁸O measurements of Jurassic (Early Pliensbachian) belemnites from the Asturian basin as a palaeo‐proxy of seawater oxygen‐isotope composition. From the combined use of the two approaches, we suggest a δ¹⁸O_w composition of about ?0.1‰ for the Jamesoni–Ibex zones. This value may have been increased by about 0.6‰ during the Davoei Zone due to the effect of waters with a different δ¹⁸O_w composition. These findings illustrate the inaccuracy of using a globally homogeneous ice‐free value of δ¹⁸O_w = ?1‰ for δ¹⁸O_carb‐based palaeotemperature reconstructions. Our data suggest that previous palaeotemperatures calculated in the region from δ¹⁸O values of belemnites may have been underestimated as the seawater oxygen isotopic composition could have been higher.     

Variability of Stable Isotope Fingerprints of the Serpulid Ficopomatus enigmaticus Within a Permanently Stratified Estuary: Implications for (Palaeo)environmental Interpretations

This paper examines how the mixing of freshwater and seawater, and related mixing of freshwater and marine particulate organic matter (POM) in the permanently stratified estuary of the River Krka, Croatia, are reflected in the stable isotope fingerprints of soft tissues and tubes of the serpulid Ficopomatus enigmaticus. The carbon stable isotope composition (δ¹³C values) of the river-borne POM is retained over long distances, causing a depletion in ¹³C of POM in brackish waters. A trophic depletion in ¹³C was recorded in serpulid soft tissues. The serpulid carbonate tubes were depleted in ¹³C even at locations with salinity close to that of the sea and were subject to large isotope fractionation between dissolved inorganic C (DIC) and carbonate caused by vital effects, making carbonate depleted in ¹³C by several per mil compared with DIC. These effects, though large in the freshwater zone, fade towards the sea. The carbonate δ¹⁸O values of tubes reflect the δ¹⁸O values of the water. The temperature-related differences in δ¹⁸O values of tubes from different sites are masked by source-related differences in the δ¹⁸O values of water arising from mixing of freshwater and seawater in the estuary. Therefore, in serpulide tubes, the terrestrial component can easily be overestimated because of vital effects during biomineralisation and trophic depletion in ¹³C in freshwater and brackish environments.     

Calibration of the carbonate ‘clumped isotope’ paleothermometer for otoliths

Paleothermometry is an essential tool for understanding past changes in climate. The ‘carbonate clumped isotope thermometer’ is a temperature proxy related to ordering of ¹³C and ¹⁸O in the carbonate lattice (based on measurements of ¹³C¹⁸O¹⁶O in CO₂ produced by acid digestion of carbonate). This thermometer has been previously calibrated for inorganic calcite and aragonitic corals [Ghosh P., Adkins J., Affek H., Balta B., Guo W. F., Schauble E. A., Schrag D., and Eiler J. M. (2006) C-13-O-18 bonds in carbonate minerals: a new kind of paleothermometer. Geochim. Cosmochim. Acta70 (6), 1439-1456]. Here we determine the relationship between growth temperatures of aragonitic fish otoliths and abundances of ¹³C¹⁸O¹⁶O produced by acid digestion of those otoliths. Our calibration is based on analyses of otoliths from six species from four genera of modern fish sampled from a latitudinal transect of the Atlantic Ocean between 54° S and 65° N, plus one species from the tropical western Pacific. The temperatures at which fish otoliths precipitated were estimated by the mean temperature in the waters in which they lived, averaged over their estimated lifetimes. Estimated growth temperatures of our samples vary between 2 and 25 °C. Our results show that the abundance of ¹³C¹⁸O¹⁶O in CO₂ produced by acid digestion of fish otolith aragonite is a function of growth temperature, following the relationship: , where Δ₄₇ is the enrichment, in per mil, of ¹³C¹⁸O¹⁶O in CO₂ relative to the amount expected for a stochastic (random) distribution of isotopes among all CO₂ isotopologues, and T is the temperature in Kelvin. This relationship closely approaches that previously documented for inorganic calcite and aragonitic coral (Ghosh et al., 2006).     

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.     

Spatial variability of watermass conditions within the European Epicontinental Seaway during the Early Jurassic (Pliensbachian–Toarcian)

In order to constrain spatial variability in watermass conditions within the European Epicontinental Seaway prior to, during and after the Toarcian Oceanic Anoxic Event, carbon (δ¹³C_bel, δ¹³C_carb) and oxygen (δ¹⁸O_bel, δ¹⁸O_carb) isotope records were obtained from three sections in the Grands Causses Basin (southern France). These data were then compared with similar records along a north–south transect across the European Epicontinental Seaway. As the conclusions reached here strongly depend on the reliability of belemnite calcites as archives of palaeoceanographic changes, an attempt was made to improve the understanding of isotope signals recorded in belemnite calcite. Intra‐rostral carbon and oxygen‐isotope data from six belemnite specimens belonging to the genus Passaloteuthis were collected. Intra‐rostral carbon‐isotopes are influenced by vital effects, whereas oxygen‐isotopes reflect relative changes in temperature and salinity. Palaeotemperatures calculated from δ¹⁸O_bel‐isotope records from the Grands Causses Basin confirm relatively low temperatures throughout the Late Pliensbachian. Similar cool water conditions have previously been shown in Germany, England, Spain and Portugal. A temperature increase of up to 6 °C is observed across the Pliensbachian–Toarcian boundary. A pronounced negative shift of at least ?3‰ (Vienna‐Pee Dee Belemnite) is recorded in bulk carbonate carbon during the lower Harpoceras serpentinum zone, typical of the Toarcian Oceanic Anoxic Event. Before and after the Toarcian Oceanic Anoxic Event, a good correlation between δ¹³C_carb and δ¹³C_bel exists, indicating well‐ventilated bottom‐waters and normal marine conditions. Instead, data for the Toarcian Oceanic Anoxic Event indicate the development of a strong north–south gradient in salinity stratification and surface‐water productivity for the Western Tethyan realm. This study thus lends further support to a pronounced regional overprint on carbon and oxygen‐isotope records in epicontinental seaways.     

C-O bonds in carbonate minerals: A new kind of paleothermometer

The abundance of the doubly substituted CO₂ isotopologue, ¹³C¹⁸O¹⁶O, in CO₂ produced by phosphoric acid digestion of synthetic, inorganic calcite and natural, biogenic aragonite is proportional to the concentration of ¹³C-¹⁸O bonds in reactant carbonate, and the concentration of these bonds is a function of the temperature of carbonate growth. This proportionality can be described between 1 and 50 °C by the function: Δ₄₇ = 0.0592 · 10⁶ · T⁻² − 0.02, where Δ₄₇ is the enrichment, in per mil, of ¹³C¹⁸O¹⁶O in CO₂ relative to the amount expected for a stochastic (random) distribution of isotopes among all CO₂ isotopologues, and T is the temperature in Kelvin. This relationship can be used for a new kind of carbonate paleothermometry, where the temperature-dependent property of interest is the state of ordering of ¹³C and ¹⁸O in the carbonate lattice (i.e., bound together vs. separated into different CO₃²⁻ units), and not the bulk δ¹⁸O or δ¹³C values. Current analytical methods limit precision of this thermometer to ca. ± 2 °C, 1σ. A key feature of this thermometer is that it is thermodynamically based, like the traditional carbonate-water paleothermometer, and so is suitable for interpolation and even modest extrapolation, yet is rigorously independent of the δ¹⁸O of water and δ¹³C of DIC from which carbonate grew. Thus, this technique can be applied to parts of the geological record where the stable isotope compositions of waters are unknown. Moreover, simultaneous determinations of Δ₄₇ and δ¹⁸O for carbonates will constrain the δ¹⁸O of water from which they grew.     

Oxygen isotope compositions of phosphate from arvicoline teeth and Quaternary climatic changes, Gigny, French Jura

Oxygen isotope compositions of biogenic phosphates from mammals are widely used as proxies of the isotopic compositions of meteoric waters that are roughly linearly related to the air temperature at high- and mid-latitudes. An oxygen isotope fractionation equation was determined by using present-day European arvicoline (rodents) tooth phosphate: δ¹⁸O_p = 20.98(±0.59) + 0.572(±0.065) δ¹⁸O_w. This fractionation equation was applied to the Late Pleistocene karstic sequence of Gigny, French Jura. Comparison between the oxygen isotope compositions of arvicoline tooth phosphate and Greenland ice core records suggests to reconsider the previously established hypothetical chronology of the sequence. According to the δ¹⁸O value of meteoric water-mean air temperature relationships, the δ¹⁸O value of arvicoline teeth records variations in mean air temperatures that range from 0° to 15°C.     

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.     

C-O isotope signatures and ‘clumped isotope’ thermometry in foraminifera and coccoliths

Accurate constraints on past ocean temperatures and compositions are critical for documenting climate change and resolving its causes. Most proxies for temperature are not thermodynamically based, appear to be subject to biological processes, require regional calibrations, and/or are influenced by fluid composition. As a result, their interpretation becomes uncertain when they are applied in settings not necessarily resembling those in which they were empirically calibrated. Independent proxies for past temperature could provide an important means of testing and/or expanding on existing reconstructions. Here we report measurements of abundances of stable isotopologues of calcitic and aragonitic benthic and planktic foraminifera and coccoliths, relate those abundances to independently estimated growth temperatures, and discuss the possible scope of equilibrium and kinetic isotope effects. The proportions of ¹³C-¹⁸O bonds in these samples exhibits a temperature dependence that is generally similar to that previously been reported for inorganic calcite and other biologically precipitated carbonate-containing minerals (apatite from fish, reptile, and mammal teeth; calcitic brachiopods and molluscs; aragonitic coral and mollusks). Most species that exhibit non-equilibrium ¹⁸O/¹⁶O (δ¹⁸O) and ¹³C/¹²C (δ¹³C) ratios are characterized by ¹³C-¹⁸O bond abundances that are similar to inorganic calcite and are generally indistinguishable from apparent equilibrium, with possible exceptions among benthic foraminiferal samples from the Arctic Ocean where temperatures are near-freezing. Observed isotope ratios in biogenic carbonates can be explained if carbonate minerals generally preserve a state of ordering that reflects the extent of isotopic equilibration of the dissolved inorganic carbon species.     

Oxygen and carbon stable isotopes of modern land snail shells as environmental indicators from a low-latitude oceanic island

Land snails provide a unique opportunity to study terrestrial paleoenvironments because their shells, which are generally highly abundant and well-preserved in the fossil record, contain a temporal record of environmental change in the form of isotope codes. To evaluate the utility of this approach for a low-latitude oceanic setting, 207 modern shells of 18 species of land snail were analyzed for their oxygen and carbon isotope composition along a north and south facing altitudinal gradient (10-2160 m a.s.l.) in Tenerife Island (∼28°N) of the Canary Archipelago.Shells collected at each locality showed a relatively large range in isotope composition which was greater along the south facing transect (drier and hotter), suggesting that the variance in shell isotope values may be related to water-stress. Although pooled isotope values did not generally show strong relationships with environmental variables (i.e., altitude, temperature and precipitation), mean isotope values were strongly associated with some climatic factors when grouped by site. The mean δ¹⁸O value of the shell (δ¹⁸O_shell) by site displayed a negative correlation with elevation, which is consistent with the positive relationship observed between temperature and the δ¹⁸O value of rain (δ¹⁸O_rain). Calculated δ¹⁸O values of the snail body water (δ¹⁸O_body) derived from observed temperatures and δ¹⁸O_shell values (using the equation of Grossman and Ku [Grossman E. L. and Ku T. L. (1986) Oxygen and carbon isotope fractionation in biogenic aragonite. Chem. Geol. (Isotope Geosci. Sec.)59, 59-74]) displayed a trend with respect to altitude that was similar to measured and hypothetical δ¹⁸O values for local rain water. The calculated δ¹⁸O_body values from the shell declined 0.17‰ (VSMOW) per 100 m, which is consistent with the “altitude effect” observed for tropical rains in Western Africa, and it correlated negatively with rainfall amount. Accordingly, lower δ¹⁸O_shell values indicate lower temperatures, lower δ¹⁸O_rain values and possibly, higher rainfall totals. A positive correlation between the mean δ¹³C values of shells (δ¹³C_shell) and plants by site suggests that shells potentially record information about the surrounding vegetation. The δ¹³C_shell values varied between −15.7 and −0.6‰ (VPDB), indicating that snails consumed C₃ and C₄/CAM plants, where more negative δ¹³C_shell values probably reflects the preferential consumption of C₃ plants which are favored under wetter conditions. Individuals with more positive δ¹³C_shell values consumed a larger percentage of C₄ plants (other potential factors such as carbonate ingestion or atmospheric CO₂ contribution were unlikely) that were more common at lower elevations of the hotter and drier south facing transect. The relatively wide range of shell isotope values within a single site requires the analysis of numerous shells for meaningful paleoclimatic studies. Although small differences were observed in isotope composition among snail species collected at a single sampling site, they were not significant, suggesting that isotope signatures extracted from multi-taxa snail data sets may be used to infer environmental conditions over a broad range of habitats.     

Carbonate clumped isotope thermometry of deep-sea corals and implications for vital effects

Here we calibrate the carbonate clumped isotope thermometer in modern deep-sea corals. We examined 11 specimens of three species of deep-sea corals and one species of a surface coral spanning a total range in growth temperature of 2-25 °C. External standard errors for individual measurements ranged from 0.005‰ to 0.011‰ (average: 0.0074‰) which corresponds to ∼1-2 °C. External standard errors for replicate measurements of Δ₄₇ in corals ranged from 0.002‰ to 0.014‰ (average: 0.0072‰) which corresponds to 0.4-2.8 °C. We find that skeletal carbonate from deep-sea corals shows the same relationship of Δ₄₇ (the measure of ¹³C-¹⁸O ordering) to temperature as does inorganic calcite. In contrast, the δ¹³ C and δ¹⁸O values of these carbonates (measured simultaneously with Δ₄₇ for every sample) differ markedly from equilibrium with seawater; i.e., these samples exhibit pronounced ‘vital effects’ in their bulk isotopic compositions. We explore several reasons why the clumped isotope compositions of deep-sea coral skeletons exhibit no evidence of a vital effect despite having large conventional isotopic vital effects.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

CO clumping in speleothems: Observations from natural caves and precipitation experiments

The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ¹⁸O. Interpreting speleothem δ¹⁸O records in terms of absolute paleotemperatures and δ¹⁸O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ₄₇ (a geochemical variable reflecting the statistical overabundance of ¹³C¹⁸O bonds in CO₂ evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ₄₇ value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation.Here we report Δ₄₇ values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ₄₇ and heavier δ¹⁸O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ₄₇ disequilibrium and that of δ¹⁸O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ¹⁸O and Δ₄₇ values, probably inherited from prior degassing within the cave system.In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ₄₇ in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ₄₇ in inorganic carbonates.     

A model for oxygen and sulfur isotope fractionation in sulfate during bacterial sulfate reduction processes

We present a model of bacterial sulfate reduction that includes equations describing the fractionation relationship between the sulfur and the oxygen isotope composition of residual sulfate (δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}) and the amount of residual sulfate. The model is based exclusively on oxygen isotope exchange between cell-internal sulfur compounds and ambient water as the dominating mechanism controlling oxygen isotope fractionation processes. We show that our model explains δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns observed from natural environments and from laboratory experiments, whereas other models, favoring kinetic isotope fractionation processes as dominant process, fail to explain many (but not all) observed δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns. Moreover, we show that a “typical” δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} slope does not exist. We postulate that measurements of δ³⁴S_{SO4_residual} and δ¹⁸O_{SO4_residual} can be used as a tool to determine cell-specific sulfate reduction rates, oxygen isotope exchange rates, and equilibrium oxygen isotope exchange factors. Data from culture experiments are used to determine the range of sulfur isotope fractionation factors in which a simplified set of equations can be used. Numerical examples demonstrate the application of the equations. We postulate that, during denitrification, the oxygen isotope effects in residual nitrate are also the result of oxygen isotope exchange with ambient water. Consequently, the equations for the relationship between δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}, and the amount of residual sulfate could be modified and used to calculate the fractionation-relationship between δ¹⁵N_{NO3_residual}, δ¹⁸O_{NO3_residual}, and the amount of residual nitrate during denitrification.     

Mixing of magmatic CO2 into volcano groundwater flow at Aso volcano assessed combining carbon and water stable isotopes

To understand deep groundwater flow systems and their interaction with CO₂ emanated from magma at depth in a volcanic edifice, deep groundwater samples were collected from hot spring wells in the Aso volcanic area for hydrogen, oxygen and carbon isotope analyses and measurements of the stable carbon isotope ratios and concentrations of dissolved inorganic carbon (DIC). Relations between the stable carbon isotope ratio (δ¹³C_DIC) and DIC concentrations of the sampled waters show that magma-derived CO₂ mixed into the deep groundwater. Furthermore, groundwaters of deeper areas, except samples from fumarolic areas, show higher δ¹³C_DIC values. The waters' stable hydrogen and oxygen isotope ratios (δD and δ¹⁸O) reflect the meteoric-water origin of that region's deep groundwater. A negative correlation was found between the altitude of the well bottom and the altitude of groundwater recharge as calculated using the equation of the recharge-water line and δD value. This applies especially in the Aso-dani area, where deeper groundwater correlates with higher recharge. Groundwater recharged at high altitude has higher δ¹³C_DIC of than groundwater recharged at low altitude, strongly suggesting that magmatic CO₂ is present to a much greater degree in deeper groundwater. These results indicate that magmatic CO₂ mixes into deeper groundwater flowing nearer the magma conduit or chamber.     

Genesis and evolution of high-pCO2 groundwaters of the Mukhen spa (Russian Far East)

We present the chemical and isotope compositions of the water and gas phases of the unique Mukhen cold high-pCO₂ spa. Estimated 5¹⁸O, 5D, and 5¹³C_tic values and data on geology and hydrogeology of the studied area indicate that the source of the groundwaters is meteoric waters, whereas carbon dioxide is of deep genesis and numerous regional faults are gas-feeding channels. Calculations of equilibrium reactions in the water-rock system show that the upper-aquifer waters (HCO₃-Ca-Mg) with low TDS are undersaturated with carbonate minerals, montmorillonites, and aluminosilicates but are oversaturated with kaolinite, whereas the lower-aquifer waters (HCO3-Na) with high TDS are oversaturated with calcite, dolomite, and clay minerals but are undersaturated with main aluminosilicates. We propose a new concept of the formation of these groundwaters, demonstrating that long interaction between rocks and groundwaters in the presence of CO₂ and considerable precipitation of secondary minerals are responsible for the high TDS of the lower-aquifer waters (up to 14 g/L) and their geochemical type (HCO₃-Na) and unusual isotope composition (5¹⁸O = -25.2%c, 5D = -69.0%c).     

Determining the O/O ratio of water using a water-CO2 equilibration method: Application to glacial-interglacial changes in O-excess from the Dome Fuji ice core, Antarctica

Recent studies show that oxygen three isotope measurement (¹⁶O, ¹⁷O, and ¹⁸O) of water provides additional information for investigating the hydrological cycle and paleoclimate. For determining the ¹⁸O/¹⁶O value of water, a conventional CO₂-water equilibration method involves measurement of the ratios of CO₂ isotopologues which were equilibrated with water. However, this long-established technique was not intended to measure the ¹⁷O/¹⁶O ratio, primarily because the historic ion correction scheme does not allow for possible deviations from a fixed (and mass-dependent) relationship between ¹⁷O/¹⁶O and ¹⁸O/¹⁶O isotope ratios. Here, we propose an improved method for obtaining the ¹⁷O/¹⁶O isotope ratio of fresh water by the equilibration method and measurement of the 45/44 CO₂ ion abundance ratio. Equations which we formulated for ¹⁷O/¹⁶O measurement have two features: first, instead of absolute isotope ratio (R), all equations are formulated in δ values, measured by isotope ratio mass spectrometry. Second, we include two “assigned” δ values of water standards in the equations, because the δ¹⁸O are commonly measured against two working standards to normalize the span of the δ scale. This approach clarifies that the contribution from ¹⁷O (¹²C¹⁶O¹⁷O⁺) to the molecular ion current at mass-to-charge ratio m/z 45 signal depends not on the absolute ¹³C/¹²C ratio, but on the relative δ¹³C differences between the working standards and the sample. The pH value of water affects δ¹⁷O estimation because δ¹³C of CO₂ was changed in the water-CO₂ system. We reevaluated this effect using a set of equations, which explicitly includes CO₂ partial pressure effect on pH value. Our new estimation of pH effect is significantly smaller than previously reported value, but it does not alter the main conclusions in the previous study. The method was verified by δ¹⁷O measurements of an international standard reference water (GISP) provided by the IAEA. We applied the method to investigate ¹⁷O-excess of the ice core drilled at the Dome Fuji station, Antarctica. A total of 1320 samples from a 130 m section around Marine Isotope Stage 9.3 (∼330,000 years before present) were measured. The error of a measurement for δ¹⁷O is 0.175‰ and that of ¹⁷O-excess is 184 per meg. Although these analytical uncertainties hampered accurate estimation of the changes in ¹⁷O-excess, the averaged data indicate that ¹⁷O-excess around MIS 9.3 was higher than during the subsequent glacial period. This approach can be applied only to fresh water samples, and additional improvements will be needed to measure samples which contains significant amount of carbonate minerals.     

Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.