Oxygen Isotope Ratio Measurements Research Articles

Comet 81P/Wild 2 dust impactors of Stardust turnip-like tracks analogous to cluster IDPs

We measured oxygen isotope ratios of 16 silicate fragments from seven aerogel tracks (turnip-like type B tracks 77, 149, 172, 191, and 220; carrot-like type A tracks 22 and 175) of the comet 81P/Wild 2 collector from NASA’s Stardust mission using secondary ion mass spectrometry. Thirteen were prepared by ultramicrotomy; three from track 220 were prepared by sputtering resin blocks using a SIMS Kohler beam, a new procedure aiming to mine as many cometary particles encased in aerogel/resin as possible. Combining new and literature results, we recognized that most silicate fragments of individual type B tracks have diverse mineralogy but consistent mass-independent fractionation of oxygen isotopes (Δ17O = δ17O − 0.52 × δ18O). These observations suggest that their impactors are loosely bound aggregates of unequilibrated materials originating mainly from similar protoplanetary disk regions, resembling the cluster IDP U2-20-GCA. Furthermore, silicate fragments from type A track 22 have almost identical mineralogy and Δ17O values, confirming that its impactor is a single chondrule-like fragment. The terminal particle of type A track 175 is pure forsterite with Δ17O of ∼ –23 ‰.Six iron-rich fragments of this study have positive oxygen isotope ratios (Δ17O∼ +2 ‰) and ordinary chondrite chondrule-like olivine compositions. Together with five similar fragments in the literature, a unique population (Mg# ≤ 86) of Wild 2 fragments that resemble chondrules from the inner solar system (O-E-R) chondrites or the outer solar system CH-CB chondrites was identified. The remaining 16O-poor Wild 2 fragments are Mg# ≥ 79 silicates with Δ17O ∼ –2 ‰ and a small amount of Mg# ≤ 79 silicates with Δ17O ∼ 0 ‰, which are most consistent with CR chondrite chondrules. Thus, we conclude that in addition to the possible major source of CR chondrite chondrule-like materials, the inner solar system or CH-CB chondrule-like materials are a minor component of comet Wild 2, like the cluster IDP U2-20-GCA.

Long-term performance of simultaneous measurement of stable isotopes of oxygen and carbon in cellulose with a high-temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry system at the Institute for Geological and Geochemical Research

AbstractA high-temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry system was established at the Institute for Geological and Geochemical Research in 2013. A dedicated field of application of the system is the simultaneous measurement of stable carbon and oxygen isotope ratios in the cellulose of modern, relict and subfossil plant tissues and sediments. The measurement protocol was fine-tuned during the first year of operation and documented in detail in this report. To quantify the long-term reproducibility of the simultaneous measurement of stable isotopes of oxygen and carbon in cellulose, a 2σ range inferred from repeated measurements of a Quality Assurance standard can be recommended: 0.16 and 0.20‰, for δ13C and δ18O, respectively. An extensive set of samples with known pyrolysis-based δ13C data was analyzed in combustion mode and the paired results were used to assess the necessity of adjustment of the pyrolysis-based δ13C measurements. The variances of the two datasets were not significantly different; the slope (intercept) of the regression was indistinguishable from unity (zero), suggesting that probably owing to the relatively frequent cleaning of the pyrolysis furnace, pyrolysis-based δ13C data neither suffer from a variance bias nor require a specific adjustment.

Salinity spatial patterns in Mediterranean coastal areas: The legacy of historical water infrastructures

Mediterranean coastal areas have been occupied and developed intensively for a long time facing issues related to agricultural production, urbanization, tourism, preservation of natural resources often linked to salinity. This article explores the relationship between historical land planning and water management, and current soil and water salinity to gain insights into future projections.Soil samples (1185) were collected in a coastal plain of 114 km2 in the south of France and saturated paste extract Electrical Conductivity (ECsp) was deduced from 1:5 dilution. Soil salinity exhibits a wide range of variation (from 0.54 to 113.1 mS cm−1) and spatial patterns. ECsp is significantly different among soil types, higher at depth than at the surface and influenced by the distance to ancient water infrastructures (Pettitt test). Surface water and shallow groundwater samples were collected for trace element concentrations and Oxygen (18O/16O) isotope ratio measurements. The geochemical signatures indicate a mixture between surface freshwater and seawater, reveal the presence of over-salted seawater and a stratification of salinity from the surface to the depth.Results suggest that groundwater is the source of soil salinity, and illustrate the long-term impact of old water infrastructures. Less saline soils are found near the freshwater supply channel (constructed from 15th to 18th), while more saline soils are located near drainage channels. The presence of over-salted water reflects temporal evolution of the plain over the last few centuries (initially under seawater, gradually filled in, presence of ponds and salt works that have now disappeared). The current soil salinity patches continue to be a visible reminder of this evolution. The trend towards desalinization of the plain over the last few centuries has been made possible by massive freshwater inflows, which are now under threat due to the general decrease of water resources availability.

Optimization of a Picarro L2140-i cavity ring-down spectrometer for routine measurement of triple oxygen isotope ratios in meteoric waters

Abstract. The demanding precision of triple oxygen isotope (Δ17O) analyses in water has restricted their measurement to dual-inlet mass spectrometry until the recent development of commercially available infrared laser analyzers. Laser-based measurements of triple oxygen isotope ratios are now increasingly performed by laboratories seeking to better constrain the source and history of meteoric waters. However, in practice, these measurements are subject to large analytical errors that remain poorly documented in scientific literature and by instrument manufacturers, which can effectively restrict the confident application of Δ17O to settings where variations are relatively large (∼ 25–60 per meg). We present our operating method of a Picarro L2140-i cavity ring-down spectrometer (CRDS) during the analysis of low-latitude rainwater where confidently resolving daily variations in Δ17O (differences of ∼ 10–20 per meg) was desired. Our approach was optimized over ∼ 3 years and uses a combination of published best practices plus additional steps to combat spectral contamination of trace amounts of dissolved organics, which, for Δ17O, emerges as a much more substantial problem than previously documented, even in pure rainwater. We resolve the extreme sensitivity of the Δ17O measurement to organics through their removal via Picarro's micro-combustion module, whose performance is evaluated in each sequence using alcohol-spiked standards. While correction for sample-to-sample memory and instrumental drift significantly improves traditional isotope metrics, these corrections have only a marginal impact (0–1 per meg error reduction) on Δ17O. Our post-processing scheme uses the analyzer's high-resolution data, which improves δ2H measurement (0.25 ‰ error reduction) and allows for much more rich troubleshooting and data processing compared to the default user-facing data output. In addition to competitive performance for traditional isotope metrics, we report a long-term, control standard root mean square error for Δ17O of 12 per meg. Overall performance (Δ17O error of 6 per meg, calculated by averaging three replicates spread across distinct, independently calibrated sequences) is comparable to mass spectrometry and requires only ∼ 6.3 h per sample. We demonstrate the impact of our approach using a rainfall dataset from Uganda and offer recommendations for other efforts that aim to measure meteoric Δ17O via CRDS.

Gradual warming prior to the end‐Permian mass extinction

AbstractThe biggest known mass extinction in the history of animal life occurred at the Permian–Triassic boundary and has often been linked to global warming. Previous studies have suggested that a geologically rapid (<40 kyr) temperature increase of more than 10°C occurred simultaneously with the main extinction pulse. This hypothesis is challenged by geochemical and palaeontological data indicating profound environmental perturbations and a temperature rise prior to the main extinction. Using secondary ion mass spectrometry (SIMS), we measured oxygen isotope ratios from Changhsingian (late Permian) ostracods of north‐western Iran. Our data show that ambient seawater temperature began to rise at least 300 kyr prior to the main extinction event. Gradual warming by approximately 12°C was probably responsible for initial environmental degradation that eventually culminated in the global end‐Permian mass extinction.

Influence of δ18 O of water on measurements of δ18 O of nitrite and nitrate.

Oxygen isotope ratio measurements of NO2 - and NO3 - by the azide method and denitrifier method are sensitive to the δ18 O value of the sample water. However, the influence of δ18 OH2O on those measurements has not been quantitatively evaluated and documented so far. Therefore, we investigated the influence of δ18 OH2O of a sample on the δ18 O analysis of NO2 - and NO3 - . We prepared NO2 - and NO3 - standards (with known δ18 ONO2- and δ18 ONO3- values) dissolved in waters having different δ18 OH2O values (δ18 OH2O = -12.6, 25.9, 56.7, and 110.1‰). Nitrite and nitrate were converted into N2 O using the azide method and the denitrifier method, respectively. The isotope ratios of the generated N2 O were measured with a Sercon purge-and-trap gas chromatography/isotope ratio mass spectrometry (PT-GC/IRMS) system. The measured δ18 O values of the produced N2 O were plotted against known δ18 ONO2- and δ18 ONO3- values to evaluate the influence of exchange of an oxygen atom with H2 O during the conversion of NO2 - into N2 O and NO3 - into N2 O, respectively. The degree of oxygen isotope exchange was 10.8 ± 0.3% in the azide method and 5.5 ± 1.0% in the denitrifier method, indicating that the azide method is more susceptible to artifacts arising from differences in the δ18 OH2O value of water than the denitrifier method. Thus, the intercept of the standard calibration curve must be corrected to account for differences in δ18 OH2O . Abiotic NO2 -H2 O equilibrium isotope effect experiments yielded a rate constant of (1.13 ± 007) × 10-2 (h-1 ) and an equilibrium isotope effect of 11.9 ± 0.1‰ under the condition of pH = 7.5, 30°C, and 2.5% salinity. Oxygen isotope ratio measurements of NO2 - by the azide method are highly sensitive to δ18 OH2O as a result of significant oxygen isotope exchange between NO2 - and H2 O. Therefore, to obtain the most accurate measurements water with the same δ18 OH2O value as that of the sample must be used to make the NO2 - and NO3 - standards.

Oxygen isotope study of the Asuka-881020 CH chondrite I: Non-porphyritic chondrules

We measured oxygen isotope ratios and major elemental compositions of non-porphyritic chondrules and lithic fragments with various textures and chemical compositions in the Asuka-881020 CH chondrite. The oxygen isotope ratios plot along the primitive chondrule mineral line with Δ17O (=δ17O – 0.52 × δ18O) values from ∼−21‰ to +5‰. The Δ17O values increase with decreasing Mg# (=molar [MgO]/[MgO + FeO]%) from 99.6 to 58.5, similarly to the Δ17O-Mg# trends for the chondrules in other carbonaceous chondrites.Most of the measured objects (non-porphyritic chondrules and lithic fragments) including chondrules analyzed in the previous studies are classified into three groups based on the Δ 17O values and chemistry; the −2.3‰ group with FeO-poor compositions (the most abundant group), the +1.4‰ group with FeO-rich compositions, and the −6.3‰ group with FeO-poor compositions. Skeletal olivine and magnesian cryptocrystalline (MgCC) chondrules and MgCC chondrule fragments, which are the −2.3‰ group objects, may have formed via fractional condensation in the isotopically uniform gaseous environment with Δ 17O of −2.3‰. When silica-normative materials condensed from gas at ∼1200 K, 16O-rich refractory solids, similar to Ca-Al-rich inclusions, were incorporated into the environment. The silica-normative materials that condensed onto the 16O-rich refractory solids were reheated at 1743–1968 K and formed cristobalite-bearing chondrules with Δ17O of ∼−6‰. This scenario can explain the absence of silica-bearing chondrules in the −2.3‰ group and refractory element abundances in the cristobalite-bearing chondrules as high as those in the MgCC chondrules.Refractory element abundances of the +1.4‰ group objects decrease from FeO-Al-rich and ferroan CC (FeCC) chondrules to FeCC chondrule fragments to FeNi metal-bearing to silica-bearing chondrules. This suggests the formation via fractional condensation in the isotopically uniform gaseous environment. The Δ17O values and FeO-rich compositions of this group could be explained by an addition of 16O-poor water ice as an oxidant to the relatively 16O-rich solids with Δ17O of −2.3‰, which may also explain existence of some MgCC chondrules and fragments with intermediate Δ17O values between −2.3‰ and +1.4‰. The immiscibility textures in the silica-bearing chondrules suggest a reheating event at a temperature of >1968 K after condensation of silica-normative materials. Thus, the non-porphyritic chondrules and fragments in CH and CB chondrites, which are classified into three distinct Δ17O groups, require multiple chondrule-forming environments and heating events. Energy source for the heating events could be either impact plume and/or other dynamical processes in the protoplanetary disk, though a single heating event would not fully explain observed chemical and isotope signatures in these non-porphyritic chondrules.

Calibration of shell δ18O from the common whelk Buccinum undatum highlights potential for palaeoenvironmental reconstruction

The common whelk, Buccinum undatum, is a commercially important gastropod found throughout the North Atlantic. One method of age and life history analysis for gastropod species is the use of oxygen isotope ratio (δ18O) measurements from their shells, which is a well-established technique for the reconstruction of historical seawater temperatures at the time of shell biomineralization. Palaeotemperature calibrations have been developed for different types of calcium carbonate as well as species-specific equations to produce the most accurate seawater temperature reconstructions. Here we investigate the four-layer internal structure of B. undatum shells and confirm an aragonite composition using Micro-Raman Spectroscopy (MRS). We then calibrate a species-specific palaeotemperature equation for this gastropod species. This was achieved through the isotopic analysis of shells from laboratory reared specimens of known provenance reared at specific seawater temperatures to produce the following:t(°C) = 14.96 (± 0.15) – 4.94 (± 0.22) x (δ18Oshell – δ18Owater)The calibrated equation differs significantly from previously published data derived from both aragonite and calcite. An offset of 1.04‰ (± 0.41‰) was discovered between observed δ18OShell values and those expected under equilibrium, suggesting a species-specific vital effect. The calibrated equation was used to reconstruct accurate, high resolution historical seawater temperatures from three sites across the U.K. (Shetland, the Menai Strait and Jersey). With this new accurate calibration, both modern and fossil B. undatum shells now have the potential to be employed as high-resolution archives of recent and historical seawater temperature.

Protocols for in situ measurement of oxygen isotopes in goethite by ion microprobe

We present protocols for high-spatial resolution measurement of oxygen isotope ratios of goethite (α-FeOOH) with the Sensitive High Mass Resolution Ion Microprobe – Stable Isotopes (SHRIMP-SI) and propose a natural sample as a potential goethite reference material (RM) for ion microprobe analysis. We assess the effects of goethite chemical composition, crystallographic orientation, and texture on the accuracy and repeatability of SHRIMP-SI δ18O (δ18OSIMS) results. Synthetic goethites evaluated as potential δ18OSIMS RM are powdery, porous, and finely crystalline; they do not yield repeatable results. A dense colloform goethite from the Capão topaz mine, Minas Gerais, Brazil, fulfills major prerequisites: it is stoichiometrically relatively pure, yields repeatable oxygen isotope results, and occurs in abundance to produce a RM for long-term use. We use an average laser fluorination δ18OLF-VSMOW value of −17.3 ± 0.3‰ (1SD) obtained for five aliquots of this RM to normalize all δ18OSIMS measurements. Multiple δ18OSIMS analyses of a large fragment of the Capão L4 (CL4) RM analyzed in three different runs yield an overall repeatability of −17.3 ± 0.5‰ (2SD, n = 294) for all three runs combined. Natural variability and crystal orientation effects are the main reasons for the excess spread of the δ18OSIMS results compared to the spot internal precision (ca. 0.2‰). All δ18OSIMS analyses (n = 1027) in various aliquots of CL4, randomly oriented and analyzed in 26 sessions during eight distinct runs, yield an overall repeatability of −17.3 ± 0.7‰ (2SD), confirming that CL4 is a suitable SIMS RM. After ascertaining its suitability as a RM, we used CL4 to standardize analyses of other natural goethite samples with the SHRIMP-SI and compared δ18OSIMS and laser fluorination results to test the relationship between natural properties (e.g., porosity, minor elements substituting for Fe), preparation procedures (e.g., polish and relief), instrument conditions, and the overall precision and accuracy of the SIMS analyses. Samples containing minor elements substituting for Fe (e.g., Al, Mn, Cu, Zn, etc.) or as contaminants (e.g., Si, P) require significant matrix corrections. Because we could not find homogenous natural goethite samples showing a large range in metal concentrations, we extrapolate our calibration curves beyond the composition of our calibration goethite samples. δ18OSIMS results corrected for instrument mass fractionation (using CL4) and compositionally dependent matrix effects (using several calibration goethites of known elemental composition) are less precise but statistically indistinguishable from their laser fluorination results. However, porous samples are unsuitable for SHRIMP-SI δ18O analysis. Dense colloform samples yield repeatable results for individual growth bands, showing that the high spatial resolution, moderate precision, and speed of analysis of the SHRIMP-SI can resolve variations in oxygen isotope composition acquired during sample growth. (UTh)/He geochronology of equivalent aliquots from the same goethite samples reveal that the combination of the two methods permits the extraction of temporal variation in the isotopic compositions of meteoric solutions in the geological past.

Barium-isotopic constraints on the origin of post-Marinoan barites

Measurements of triple oxygen isotope ratios in barite horizons within post-Marinoan cap carbonates have provided some of the most compelling evidence that the Marinoan glaciation was a Snowball Earth event. However, the origin of these barite horizons remains unresolved. To constrain the Ba sources, and thus formation mechanisms of these horizons, we analyzed the Ba isotope composition of post-Marinoan barite deposits from Northwest Canada, Northern Norway, Brazil and South China. We augment these analyses with a Ba isotope survey of almost 100 modern and ancient additional barite measurements, including samples from pelagic (or ‘marine’), hydrothermal, terrestrial, Proterozoic stratiform and cold seep environments. Unlike modern cold seep or terrestrial barites, we find that globally-distributed post-Marinoan barites exhibit a relatively narrow isotopic range, suggesting a well-mixed, effectively limitless Ba source. Moreover, post-Marinoan deposits exhibit a similar mean Ba isotope composition to modern marine barites, which we interpret as evidence of a marine Ba source. Considered alongside existing geochemical, geological, and new Ba isotope survey data, we conclude that Ba in barite horizons was sourced from a well-mixed, Ba-replete but SO4-poor reservoir that accumulated during the Marinoan Snowball Earth interval. This deep Ba reservoir was then transported upward—either by ocean circulation or dolomitization of underlying cap carbonates—and was brought into contact with continental weathering-derived sulfate in a post-glacial meltwater surface layer. Thus, in addition to providing a plausible mechanism for generating globally-synchronous deposition of post-Marinoan barite horizons that reconciles all existing geochemical and geological data, our results demonstrate the utility of Ba isotopes to interrogate the origin of enigmatic barite deposits throughout the sedimentary record.

Addressing data comparability in the creation of combined data sets of bioapatite carbon and oxygen isotopic compositions

Before amalgamating published isotope data, comparability should be demonstrated. This paper compares carbon and oxygen isotopic compositions of 30 enamel samples measured by two laboratories. The aims were to see what, if any, isotopic variation was observed, to determine the causes as needed and to correct if possible. Bioapatite was acidified at 90°C in 2006 and at 26°C in 2017, while δ values were corrected via one‐point normalization in 2006 and by two‐point normalization in 2017. One case (of the 30) produced different δ values between the analysis dates, suggesting contamination. Repeated carbon isotope ratio measurements were not meaningfully different. Repeated oxygen isotope ratio measurements were significantly different, even following correction for acid‐carbonate fractionation at different temperatures and the renormalization of 2017 δ values using one point; however, differences were not meaningful for interpretations. Results were used to calculate real interpretative differences (RIDs) for comparing enamel bioapatite as 0.6‰ for δ13C values and as 1.6‰ for δ18O values.

Oxygen isotopes as a tool to quantify reservoir-scale CO2 pore-space saturation

Structural and residual trapping of carbon dioxide (CO2) are two key mechanisms of secure CO2 storage, an essential component of Carbon Capture and Storage technology. Estimating the amount of CO2 that is trapped by these two mechanisms is a vital requirement for accurately assessing the secure CO2 storage capacity of a formation, but remains a key challenge. Here, we review recent field and laboratory experiment studies and show that simple and relatively inexpensive measurements of oxygen isotope ratios in both the injected CO2 and produced water can provide an assessment of the amount of CO2 that is stored by residual and structural trapping mechanisms. We find that oxygen isotope assessments provide results that are comparable to those obtained by geophysical techniques. For the first time we assess the advantages and potential limitations of using oxygen isotopes to quantify CO2 pore-space saturation based on a comprehensive review of oxygen isotope measurements from reservoir waters and various global CO2 injection test sites. We further summarise the oxygen isotope composition of captured CO2 in order to establish the controls on this fingerprint.

Uniform Silicon Isotope Ratios Across the Milky Way Galaxy

Abstract We report the relative abundances of the three stable isotopes of silicon, 28Si, 29Si, and 30Si, across the Galaxy using the transition of silicon monoxide. The chosen sources represent a range in Galactocentric radii ( ) from 0 to 9.8 kpc. The high spectral resolution and sensitivity afforded by the Green Bank Telescope permit isotope ratios to be corrected for optical depths. The optical-depth-corrected data indicate that the secondary-to-primary silicon isotope ratios and vary much less than predicted on the basis of other stable isotope ratio gradients across the Galaxy. Indeed, there is no detectable variation in Si isotope ratios with . This lack of an isotope ratio gradient stands in stark contrast to the monotonically decreasing trend with exhibited by published secondary-to-primary oxygen isotope ratios. These results, when considered in the context of the expectations for chemical evolution, suggest that the reported oxygen isotope ratio trends, and perhaps those for carbon as well, require further investigation. The methods developed in this study for SiO isotopologue ratio measurements are equally applicable to Galactic oxygen, carbon, and nitrogen isotope ratio measurements, and should prove useful for future observations of these isotope systems.

Pyroxene standards for SIMS oxygen isotope analysis and their application to Merapi volcano, Sunda arc, Indonesia

Measurement of oxygen isotope ratios in common silicate minerals such as olivine, pyroxene, feldspar, garnet, and quartz is increasingly performed by Secondary Ion Mass Spectrometry (SIMS). However, certain mineral groups exhibit solid solution series, and the large compositional spectrum of these mineral phases will result in matrix effects during SIMS analysis. These matrix effects must be corrected through repeated analysis of compositionally similar standards to ensure accurate results. In order to widen the current applicability of SIMS to solid solution mineral groups in common igneous rocks, we performed SIMS homogeneity tests on new augite (NRM-AG-1) and enstatite (NRM-EN-2) reference materials sourced from Stromboli, Italy and Webster, North Carolina, respectively. Aliquots of the standard minerals were analysed by laser fluorination (LF) to establish their δ18O values. Repeated SIMS measurements were then performed on randomly oriented fragments of the same pyroxene crystals, which yielded a range in δ18O less than ±0.42 and ±0.58‰ (2σ) for NRM-AG-1 and NRM-EN-2, respectively. Homogeneity tests verified that NRM-AG-1 and NRM-EN-2 do not show any crystallographic orientation bias and that they are sufficiently homogeneous on the 20μm scale to be used as routine mineral standards for SIMS δ18O analysis. We subsequently tested our new standard materials on recently erupted pyroxene crystals from Merapi volcano, Indonesia. The δ18O values for Merapi pyroxene obtained by SIMS (n=204) agree within error with the LF-derived δ18O values for Merapi pyroxene but differ from bulk mineral and whole-rock data obtained by conventional fluorination. The bulk samples are offset to higher δ18O values as a result of incorporation of mineral and glass inclusions that in part reflects crustal contamination processes. The Merapi pyroxene SIMS data, in turn, display a frequency peak at 5.8‰, which allows us to estimate the δ18O value of the primary mafic magma at Merapi to ~6.1‰ when assuming closed system differentiation.

Using oxygen isotopes to quantitatively assess residual CO2 saturation during the CO2CRC Otway Stage 2B Extension residual saturation test

Residual CO2 trapping is a key mechanism of secure CO2 storage, an essential component of the Carbon Capture and Storage technology. Estimating the amount of CO2 that will be residually trapped in a saline aquifer formation remains a significant challenge. Here, we present the first oxygen isotope ratio (δ18O) measurements from a single-well experiment, the CO2CRC Otway 2B Extension, used to estimate levels of residual trapping of CO2. Following the initiation of the drive to residual saturation in the reservoir, reservoir water δ18O decreased, as predicted from the baseline isotope ratios of water and CO2, over a time span of only a few days. The isotope shift in the near-wellbore reservoir water is the result of isotope equilibrium exchange between residual CO2 and water. For the region further away from the well, the isotopic shift in the reservoir water can also be explained by isotopic exchange with mobile CO2 from ahead of the region driven to residual, or continuous isotopic exchange between water and residual CO2 during its back-production, complicating the interpretation of the change in reservoir water δ18O in terms of residual saturation. A small isotopic distinction of the baseline water and CO2 δ18O, together with issues encountered during the field experiment procedure, further prevents the estimation of residual CO2 saturation levels from oxygen isotope changes without significant uncertainty. The similarity of oxygen isotope-based near-wellbore saturation levels and independent estimates based on pulsed neutron logging indicates the potential of using oxygen isotope as an effective inherent tracer for determining residual saturation on a field scale within a few days.

Measurement of oxygen isotope ratios ((18)O/(16)O) of aqueous O2 in small samples by gas chromatography/isotope ratio mass spectrometry.

Oxygen isotope fractionation of molecular O2 is an important process for the study of aerobic metabolism, photosynthesis, and formation of reactive oxygen species. The latter is of particular interest for investigating the mechanism of enzyme-catalyzed reactions, such as the oxygenation of organic pollutants, which is an important detoxification mechanism. We developed a simple method to measure the δ(18) O values of dissolved O2 in small samples using automated split injection for gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS). After creating a N2 headspace, the dissolved O2 partitions from aqueous solution to the headspace, from which it can be injected into the gas chromatograph. In aqueous samples of 10 mL and in diluted air samples, we quantified the δ(18) O values at O2 concentrations of 16 μM and 86 μM, respectively. The chromatographic separation of O2 and N2 with a molecular sieve column made it possible to use N2 as the headspace gas for the extraction of dissolved O2 from water. We were therefore able to apply a rigorous δ(18) O blank correction for the quantification of (18) O/(16) O ratios in 20 nmol of injected O2 . The successful quantification of (18) O-kinetic isotope effects associated with enzymatic and chemical reduction of dissolved O2 illustrates how the proposed method can be applied for studying enzymatic O2 activation mechanisms in a variety of (bio)chemical processes.

High-precision measurements of δ(17)O and (17) Oexcess of NBS19 and NBS18.

Measurements of oxygen-17 excess ((17)Oexcess) in carbonates have become of great importance. However, to compare results obtained by different laboratories, it is necessary to normalize them to international standards. With this purpose in mind, we measured accurate and high precision δ(17)O and (17)Oexcess values for NBS19 and NBS18, two international standards, for which δ(18)O values are already widely used as the references for carbonates. The measurements are based on isotopic exchange at steady state between O2 and CO2 over hot platinum sponge at 750°C. Dual-inlet isotope ratio mass spectrometry (IRMS) measurements of the δ(17)O and δ(18)O values of this O2 allow δ(17)O values of CO2 to be obtained with very high precision (0.01 to 0.03‰) and, correspondingly, accurate (17)Oexcess values with a precision of 5 per meg. We measured, for the first time, the δ(17)O values and (17)Oexcess of CO2 liberated from NBS19 at 25°C (39.196 ± 0.026; 20.276 ± 0.015‰ and -227 ± 4 per meg, respectively) and NBS18 (17.591 ± 0.041‰; 9.253 ± 0.018‰ and 3 ± 5 per meg, respectively). The values are given versus VSMOW. Accurate values of δ(17)O and (17)Oexcess of the international standards NBS19-CO2 and NBS18-CO2 are now available. The new values should be used for normalization of measured oxygen isotope ratios of carbonates to allow meaningful comparison of results among different laboratories.

Isotopic signatures in the otoliths of reef-associated fishes of southern Florida: Linkages between nursery grounds and coral reefs

Ecologically and economically important coral reef fishes are believed to migrate to reefs from juvenile nursery areas such as sea grass and mangrove habitats. Little is known about the migration corridors that exist between nursery and coral reefs, or the timing of these migrations. This study investigated the possibility of identifying connections between juvenile nursery areas and nearby coral reef adult habitats using stable isotope analysis of the otoliths of gray snapper (Lutjanus griseus) (n= 71) and yellowtail snapper (Ocyuruschrysurus) (n=60), collected from 10 sites along the Florida Keys coral reef tract in 2003. Measurements of carbon and oxygen isotope ratios were compared to existing isotopic signatures of juvenile snapper from nursery areas around southern Florida. Data showed overlap for 13C and 18Oisotope measurements for the juvenile portion of sub-adult otoliths to isotope values for the middle and lower Florida Keys regions, thereby suggesting a migratory connection. Specific nursery habitats contributed approximately 93 % of individuals sampled for yellowtail and approximately 98 % for gray snapper to the Florida Keys coral reef tract. Results from this study indicate locally important source regions and habitats for the successful recruitment of fish to the Florida Keys coral reef tract.

High-precision (143)Nd/(144)Nd ratios from NdO(+) data corrected with in-run measured oxygen isotope ratios.

The NdO(+) technique has been considerably refined in recent years for high-precision measurement of Nd isotope ratios in low-level samples (1-5 ng Nd). As oxygen isotopic compositions may vary significantly with experimental conditions such as filament material, ionization enhancer and the ambient oxygen in the ion source, great "care" should be taken for using correct oxygen isotopic compositions to do the isobaric oxide corrections for the "conventional" NdO(+) method. Our method presented here for NdO(+) data reduction and PrO(+) interference corrections uses the oxygen isotope composition determined in each cycle of the NdO(+) measurements. For that purpose, we measured the small ion signals of (150)Nd(17)O(+) and (150)Nd(18)O(+) with amplifiers equipped with 10(12) Ω feedback resistors, and those of Nd(16)O(+) ion beams with 10(11) Ω amplifiers. Using 10(12) Ω amplifiers facilitates a precise measurement of the very small (150)Nd(17)O(+) and (150)Nd(18)O(+) ion signals and calculation of highly accurate and precise (143)Nd/(144)Nd isotope ratios. The (143)Nd/(144)Nd ratios for JNdi-1 standards and several whole-rock reference materials determined with the method on 4 ng of Nd loads are consistent with previously reported values within analytical error, with internal and external precision (2 RSE and 2 RSD) of better than 20 and 30 ppm, respectively.

Sample matrix effects on measured carbon and oxygen isotope ratios during continuous-flow isotope-ratio mass spectrometry.

Continuous-flow isotope-ratio mass spectrometry (CF-IRMS) is frequently used to analyze CO2 found in media such as air, breath, and soil pore space gas with the aid of a sample preparation and transfer device such as a Gasbench II. This study investigated the effect that matrices other than helium (He) have on the measured δ(13)C and δ(18)O isotope ratios of CO2. Identical CO2 was added to sample vials with matrices of pure He, pure N2, or a 21:79 mixture of O2/N2 and analyzed by a ThermoFinnigan Delta(Plus) XP isotope-ratio mass spectrometer coupled to a ThermoFinnigan Gasbench II. Variables such as CO2 concentration, sample analysis sequence, and sample matrix removal ('blanking') through manipulation of an injection and dilution open split were tested to identify systematic isotope ratio offsets between the different matrix types. The process of blanking induced a δ(13)C and δ(18)O offset of ≤0.2‰ between otherwise identical populations of CO2 samples in He. The (13)C/(12)C and (18)O/(16)O isotope ratios of CO2 sampled from pure N2 or a mixture of O2/N2 were found to be within 0.1 to 0.2‰ of those of an identical CO2 sampled from a He matrix when N2 or O2/N2 was removed prior to transport to the mass spectrometer. The measured oxygen isotope ratios of CO2 sampled from N2 and O2/N2 varied by as much as 0.6‰ and 4‰, respectively, if matrix gas was not removed prior to ionization. Sampling CO2 from matrices similar to air does not significantly affect the measured (13)C/(12)C and (18)O/(16)O isotope ratios of CO2 when a gas-handling procedure that includes the removal of matrix gas is utilized. This procedure is much preferable to introducing matrix gas and potentially isobaric interference to the ion source.