18O In CO2 Research Articles

Atmospheric measurements of Δ17O in CO2 in Göttingen, Germany reveal a seasonal cycle driven by biospheric uptake

The triple oxygen isotope composition of tropospheric CO2 might be a promising new tracer for terrestrial gross carbon fluxes. This notion is based on global box modeling of its abundance, and on highly challenging and therefore very sparse measurements of 16O, 17O and 18O in CO2 in the lower atmosphere. Here, we present additional high-precision triple oxygen isotope measurements of ambient air CO2 sampled in Göttingen (NW Germany) over the course of 2years and of two air samples taken on top of the Brocken Mountain (1140m, NW Germany). Göttingen differs from other locations where Δ17O was measured by its proximity to both urban sources of CO2, and to extensive uptake of CO2 by vegetation. In our analysis, we specifically try to discern this latter influence on our measurements, and to distinguish it from other known sources of variation in Δ17O.Our triple oxygen isotope data are reported as Δ17O values relative to a CO2-water equilibration line with Δ17O=ln (δ17O+1)−0.5229×ln (δ18O+1). We report an average of -0.02±0.05‰ (SD) in the first year and -0.12±0.04‰ (SD) in the second year of our measurements. This year-to-year difference is higher than expected based on other available Δ17O records, but careful scrutiny of our measurement approach did not reveal obvious analytical biases, leaving this aspect of our record unexplained. After removing the year-to-year trend, our time series shows a statistically robust seasonal cycle with maximum values in June/July and an amplitude (peak-to-trough) of 0.13±0.02‰. We compare our observational data to a revised triple oxygen isotope mass balance “box” model of tropospheric CO2 where we reconcile both 18O/16O and 17O/16O fractionation processes. We also compare them to Göttingen-specific output from a three-dimensional transport model simulation of Δ17O in CO2 performed with the Tracer Model 5 (TM5). Both the modeled isofluxes at the surface, and the modeled stratospheric, fossil, and biospheric Δ17O components in the atmosphere at Göttingen confirm that the observed seasonal cycle in Δ17O is driven primarily by the seasonal cycle of gross primary productivity (GPP), and that the seasonal variations in both stratospheric transport and fossil fuel emissions play a minor role at our location. Our results therefore strengthen earlier suggestions that GPP is reflected in Δ17O, and call for more seasonally resolved measurements at continental locations like Göttingen.

Oxygen-18 isotope of breath CO₂ linking to erythrocytes carbonic anhydrase activity: a biomarker for pre-diabetes and type 2 diabetes.

Carbonic anhydrase (CA), a well-characterized metalloenzyme, is associated with oxygen-18 ( 18O)-isotopic fractionations of CO2. To investigate how CA activity links the 18O of breath CO2 to pre-diabetes (PD) and type 2 diabetes (T2D) during metabolism, we studied pre- and post-dose CA activities in erythrocytes with simultaneous monitoring of 18O/ 16O-isotope ratios of breath CO2 and thereafter elucidated potential metabolic pathways underlying CA alteration in the pathogenesis of T2D. Here we show that the post-dose CA activity in both T2D and PD was markedly enhanced, whereas the non-diabetic controls (NDC) exhibited a considerable reduction in post-dose CA activity when compared with their basal CA activities. However, T2D and PD exhibited isotopic enrichments of 18O in breath CO2, while a marked depletion of 18O in CO2 was manifested in NDC. Thus, the isotopic enrichments and depletions of 18O in breath CO2 were well correlated with the changes in CA activities for controls, PD and T2D. Our findings suggest the changes in CA activities in erythrocytes may contribute to the pathogenesis of T2D and the breath C 18O 16O regulated by the CA activity as a potential biomarker for non-invasive assessment of T2D, and thus may open a new method for treating T2D.

Decadal Δ17O record of tropospheric CO2: Verification of a stratospheric component in the troposphere

AbstractFor quantification and prediction of global warming due to anthropogenic carbon dioxide (CO2) emissions, high‐resolution determination of carbon cycle reservoir size and rates of exchange is vital. Isotope ratio measurements of 13C and 18O in CO2 have proven their utility in resolving the carbon cycle. Here we report a long‐term record of triple oxygen isotopic composition of tropospheric CO2. A presence of a steady state stratospheric component (Δ17O = ln[(δ17O + 1) − 0.522 ln(δ18O + 1)] = 0.08 ± 0.04‰) is observed in tropospheric CO2 after modeling via a long‐term spline fit of the record, adding an additional technique for quantification of CO2 fluxes. The δ18O of CO2 (measured as O2 for oxygen triple isotopic composition) from the present study is compared to the measurements of the Scripps Institute of Oceanography CO2 network (measured as CO2 for δ13C and δ18O) and found to be comparable. We note that the triple oxygen isotopic signal (Δ17O) significantly decreased to 0.02 ± 0.02‰ from the steady state value of 0.08 ± 0.04‰ during the 1997–1999 time period. The possible causes for this depletion are evaluated and discussed. An enhanced role of global primary productivity, facilitating water‐CO2 isotope exchange is possible, and future measurements and modeling strategies may develop this further.

Vehicle emissions of greenhouse gases and related tracers from a tunnel study: CO : CO<sub>2</sub>, N<sub>2</sub>O : CO<sub>2</sub>, CH<sub>4</sub> : CO<sub>2</sub>, O<sub>2</sub> : CO<sub>2</sub> ratios, and the stable isotopes <sup>13</sup>C and <sup>18</sup>O in CO<sub>2</sub> and CO

Abstract. Measurements of CO2, CO, N2O and CH4 mole fractions, O2 / N2 ratios and the stable isotopes 13C and 18O in CO2 and CO have been performed in air samples from the Islisberg highway tunnel (Switzerland). The molar CO : CO2 ratios, with an average of (4.15 ± 0.34) ppb:ppm, are lower than reported in previous studies, pointing to a reduction in CO emissions from traffic. The 13C in CO2 reflects the isotopic composition of the fuel. 18O in CO2 is slightly depleted compared to the 18O in atmospheric O2, and shows significant variability. In contrast, the δ13C values of CO show that significant fractionation takes place during CO destruction in the catalytic converter. 13C in CO is enriched by 3‰ compared to the 13C in the fuel burnt, while the 18O content is similar to that of atmospheric O2. We compute a fractionation constant of (−2.7 ± 0.7)‰ for 13C during CO destruction. The N2O : CO2 average ratio of (1.8 ± 0.2) × 10−2 ppb:ppm is significantly lower than in past studies, showing a reduction in N2O emissions likely related to improvements in the catalytic converter technology. We also observed small CH4 emissions, with an average CH4 : CO2 ratio of (4.6 ± 0.2) × 10−2 ppb:ppm. The O2 : CO2 ratios of (−1.47 ± 0.01) ppm:ppm are very close to the expected, theoretically calculated values of O2 depletion per CO2 enhancement.

Measurements of greenhouse gases and related tracers at Bialystok tall tower station in Poland

Abstract. Quasi-continuous, in-situ measurements of atmospheric CO2, O2/N2, CH4, CO, N2O, and SF6 have been performed since August 2005 at the tall tower station near Bialystok, in Eastern Poland, from five heights up to 300 m. Besides the in-situ measurements, flask samples are filled approximately weekly and measured at Max-Planck Institute for Biogeochemistry for the same species and, in addition, for H2, Ar/N2 and the stable isotopes 13C and 18O in CO2. The in-situ measurement system was built based on commercially available analysers: a LiCor 7000 for CO2, a Sable Systems "Oxzilla" FC-2 for O2, and an Agilent 6890 gas chromatograph for CH4, CO, N2O and SF6. The system was optimized to run continuously with very little maintenance and to fulfill the precision requirements of the CHIOTTO project. The O2/N2 measurements in particular required special attention in terms of technical setup and quality assurance. The evaluation of the performance after more than three years of operation gave overall satisfactory results, proving that this setup is suitable for long term remote operation with little maintenance. The precision achieved for all species is within or close to the project requirements. The comparison between the in-situ and flask sample results, used to verify the accuracy of the in-situ measurements, showed no significant difference for CO2, O2/N2, CH4 and N2O, and a very small difference for SF6. The same comparison however revealed a statistically significant difference for CO, of about 6.5 ppb, for which the cause could not be fully explained. From more than three years of data, the main features at Bialystok have been characterized in terms of variability, trends, and seasonal and diurnal variations. CO2 and O2/N2 show large short term variability, and large diurnal signals during the warm seasons, which attenuate with the increase of sampling height. The trends calculated from this dataset, over the period August 2005 to December 2008, are 2.02±0.46 ppm/year for CO2 and −23.2±2.5 per meg/year for O2/N2. CH4, CO and N2O show also higher variability at the lower sampling levels, which in the case of CO is strongly seasonal. Diurnal variations in CH4, CO and N2O mole fractions can be observed during the warm season, due to the periodicity of vertical mixing combined with the diurnal cycle of anthropogenic emissions. We calculated increase rates of 10.1±4.4 ppb/year for CH4, (−8.3)±5.3 ppb/year for CO and 0.67±0.08 ppb/year for N2O. SF6 shows only few events, and generally no vertical gradients, which suggests that there are no significant local sources. A weak SF6 seasonal cycle has been detected, which most probably is due to the seasonality of atmospheric circulation. SF6 increased during the time of our measurement at an average rate of 0.29±0.01 ppt/year.

CO2 isotopes as tracers of firn air diffusion and age in an Arctic ice cap with summer melting, Devon Island, Canada

Firn air and ice have been sampled and analyzed for trace gases (CO2, N2O, CH4, and CO) and isotopes (14C, 13C, and 18O of CO2; 3H of ice) at 3 m intervals from the surface to the depth of closure at 60 m on the Devon Island Ice Cap, a low‐elevation permanent glacier in the Canadian Arctic Islands, to investigate firn diffusion and the effects of summer melting. The 14CO2 profile from the permeable firn includes the 1963 thermonuclear peak at a depth of 53.9 ± 1.5 m. The twofold increase and rapid decay that characterize the recent atmospheric history for 14CO2 provide a robust atmospheric scenario that is used with a firn air diffusion model to inversely construct the firn diffusivity profile. The results show a permeable but essentially nondiffusive zone from 50 to 60 m depth. A firn‐ice age profile was produced from density measurements, and accumulation rates were calibrated with the depth of the 1963 thermonuclear 3H peak. The average ages for CO2 in the sampled firn air profile were determined by a new method based on the rate of 18O exchange between CO2 and the ice matrix. Calibrated with the 1963 peak for thermonuclear 14CO2, a 21.2‐year reaction halftime is calculated for exchange taking place at the firn temperature of −22.8°C on Devon. This gives an average age of 54.9 (+6.0/−12.0) years for firn air at 60 m depth in 140‐year‐old ice. Thus CO2 has a mean age 85 years younger than associated ice at the point of occlusion. The measured in firn air provides no indication of alteration by summer melting, which is attributed to a high degree of convective and diffusive flushing of the upper firn as shown by diffusion modeling. This suggests that ice sheets with summer melt layers can reliably preserve atmospheric trace gas signals.

18O composition of CO2 and H2O ecosystem pools and fluxes in a tallgrass prairie: Simulations and comparisons to measurements

AbstractIn this paper we describe measurements and modeling of 18O in CO2 and H2O pools and fluxes at a tallgrass prairie site in Oklahoma. We present measurements of the δ18O value of leaf water, depth‐resolved soil water, atmospheric water vapor, and Keeling plot δ18O intercepts for net soil‐surface CO2 and ecosystem CO2 and H2O fluxes during three periods of the 2000 growing season. Daytime discrimination against C18OO, as calculated from measured above‐canopy CO2 and δ18O gradients, is also presented. To interpret the isotope measurements, we applied an integrated land‐surface and isotope model (ISOLSM) that simulates ecosystem H218O and C18OO stocks and fluxes. ISOLSM accurately predicted the measured isotopic composition of ecosystem water pools and the δ18O value of net ecosystem CO2 and H2O fluxes. Simulations indicate that incomplete equilibration between CO2 and H2O within C4 plant leaves can have a substantial impact on ecosystem discrimination. Diurnal variations in the δ18O value of above‐canopy vapor had a small impact on the predicted δ18O value of ecosystem water pools, although sustained differences had a large impact. Diurnal variations in the δ18O value of above‐canopy CO2 substantially affected the predicted ecosystem discrimination. Leaves dominate the ecosystem 18O‐isoflux in CO2 during the growing season, while the soil contribution is relatively small and less variable. However, interpreting daytime measurements of ecosystem C18OO fluxes requires accurate predictions of both soil and leaf 18O‐isofluxes.

Oxygen isotope composition of stratospheric carbon dioxide

Heavy oxygen isotope enrichment in stratospheric CO2 has been identified in the past as a direct result of the large O3 isotope anomaly though no simultaneous measurements are known. Results from 8 stratospheric balloon flights at two latitudes are reported that provide now a complete oxygen isotope analysis of both gases. An unambiguous, very tight correlation between enrichments of 17O and 18O in CO2 has been found. The large ratio δ17O/δ18O of 1.71 ± 0.03 shows a faster transfer of 17O than of 18O into CO2 and establishes a standard throughout the lower and middle stratosphere between midlatitudes and high northern latitudes. Ozone isotope transfer can now be treated in models with reliable atmospheric data.

Carbon and Oxygen Isotope Separation by Plasma Chemical Reactions in Carbon Monoxide Glow Discharge

The separation of carbon and oxygen isotopes in CO glow discharge has been studied. The isotope enrichment in the products was measured by quadru-pole mass spectrometer. The reaction yield and empirical formula of solid phase products were determined by the gas-volumetric analysis. The stable products obtained in our experiment are CO2 and solid polymers formed on the discharge wall. The polymer consists of both carbon and oxygen and the oxygen/carbon mole ratio in the polymer is 0.35±0.05. The isotope enrichment coefficients show a strong negative dependence on discharge current though the relative reaction yields have an opposite tendency. Consequently, the maximum isotope enrichment coefficients for 13C in wall deposit of 2.31 and for 18O in CO2 of 1.37 are obtained when the discharge current and the reaction yields are minimum in our experimental range. The experimental results of isotope enrichment have been compared with theoretical values estimated by an analytical model of literature. The dilution mechanism of the isotope enrichment of stable products is inferred from the isotopic distributions of 13C and 18O in products and theoretical predictions for isotope enrichment.

18O Exchange in Suspensions of Red Blood Cells: Determination of Parameters of Mass Spectrometer Inlet System

A membrane inlet system to a mass spectrometer (MIMS) allows us to monitor the abundance of 18O in CO2 during the exchange of 18O between HCO3 −, dissolved CO2 and H2O that occurs after dissolving 18O-labelled NaHCO3 in aqueous solution. Using a mathematical model we quantitate intracellular carbonic anhydrase activity and membrane permeabilities for HCO3 −, CO2 and H2O of isolated cells or intact epithelia added to the solution. For these calculations it was necessary to determine (a) the relation between MS signal and [C18O16O], (b) MIMS response kinetics and (c) CO2 leakage during the experiment. The three parameters were determined by stepwise addition of HCl to HCO3 − solution: (a) was found to be linear, (b) response times were 7.5±2s (10°C), 4.5±1s (20°C), 3.5±0.6s (37°C), and (c) CO2 leakage was < 1‰ s−1.

A three‐dimensional synthesis study of δ18O in atmospheric CO2: 1. Surface fluxes

The isotope 18O in CO2 is of particular interest in studying the global carbon cycle because it is sensitive to the processes by which the global land biosphere absorbs and respires CO2. Carbon dioxide and water exchange isotopically both in leaves and in soils, and the 18O character of atmospheric CO2 is strongly influenced by the land biota, which should constrain the gross primary productivity and total respiration of land ecosystems. In this study we calculate the global surface fluxes of 18O for vegetation and soils using the SiB2 biosphere model coupled with the Colorado State University general circulation model. This approach makes it possible to use physiological variables that are consistently weighted by the carbon assimilation rate and integrated through the vegetation canopy. We also calculate the air‐sea exchange of 18O and the isotopic character of fossil emissions and biomass burning. Global mean values of the isotopic exchange with each reservoir are used to close the global budget of 18O in CO2. Our results confirm the fact that the land biota exert a dominant control on the δ18O of the atmospheric reservoir. At the global scale, exchange with the canopy produces an isotopic enrichment of CO2, whereas exchange with soils has the opposite effect.

Rapid, automated analysis of13C and18O of CO2 in gas samples by continuous-flow, isotope ratio mass spectrometry

A rapid automated method for isotopic analysis of 13C and 18O in CO2 has been developed. A variety of gas samples containing CO2 can be swept from serological tubes into a helium carrier flow; impurities are separated on a GC column so that a pure pulse of CO2 in He flows into the mass spectrometer. Isotopic ratio determinations are carried out as the pulse passes through the mass spectrometer, allowing a sample to be measured approximately every 4 min. A double, concentric needle-probe is used to flush the sample from the tube so that 100% sample recovery is achieved, maximizing sensitivity and preventing the possibility of fractionation. The precision of the technique, sigma(m-1), is better than 0.2% (0.0002 atom per cent excess) for 13C and 0.4% (0.83 p.p.m.) for 18O for 10 micromol of CO2 at natural abundance. Samples containing only atmospheric concentrations of CO2 can also be analyzed.

The applicability of evacuated serological tubes for the collection of breath for isotopic analysis of CO2 by isotope ratio mass spectrometry.

Stable isotope ratio mass spectrometry was used for the analysis of 13C and 18O in CO2 of human breath collected in evacuated serological tubes (Vacutainer and Venoject) and in gas sample bottles. There was a 1-2% difference between the delta 13 CPDB values obtained from breath CO2 collected in gas bottles and that collected in two batches of Vacutainer. delta 18OPDB differed between Vacutainers and gas bottles by as much as 14% and standard deviations within the two batches of Vacutainer were 0.7 and 1.8%. The poor reproducibility and accuracy for the delta 18OPDB values was caused by the presence of a contaminant which originated from the rubber septa of the Vacutainers. The results show that it is not possible to obtain delta 18OPDB values with a high degree of accuracy or precision for breath samples collected in Vacutainers. However, with selection of less contaminated or re-evacuated batches, delta 13CPDB analysis of breath CO2 in Vacutainers may provide acceptable accuracy and precision. delta 13CPDB and delta 18OPDB values measured in breath collected in non-sterile Venoject tubes were also significantly different from those obtained with gas bottles. However, the accuracy and precision of these determinations were considerably better than in sterilized Vacutainer tubes. As a result of these comparisons it is concluded that gas bottles are necessary for the full accuracy and precision of stable isotope ratio analysis mass spectrometers to be exploited in breath CO2 analysis. However, automated analysis of breath CO2 collected in non-sterile Venoject tubes will provide an accuracy and precision that is suitable for most biological studies.

Molecular basis of the oxygen exchange from CO2 catalyzed by carbonic anhydrase III from bovine skeletal muscle.

The exchange of 18O from CO2 to H2O in aqueous solution is caused by the hydration-dehydration cycle and is catalyzed by the carbonic anhydrases. In our previous studies of 18O exchange at chemical equilibrium catalyzed by isozymes I and II of carbonic anhydrase, we observed simple first-order depletion of 18O from CO2 with the 18O distribution among the species C18O18O, C16O18O, and C16O16O described by the binomial expansion (i.e., a random distribution of 18O). Using membrane-inlet mass spectrometry, we have measured 18O exchange between CO2 and H2O catalyzed by native zinc-containing and cobalt(II)-substituted carbonic anhydrase III from bovine skeletal muscle near pH 7.5. The distributions of 18O in CO2 deviate from the binomial expansion and are accompanied by biphasic 18O-exchange patterns; moreover, we observed regions in which 18O loss from CO2 was faster than 18O loss from HCO3-. These data are interpreted in terms of a model that includes 18O loss from an enzyme-substrate or intermediate complex. We conclude that more than one 18O can be lost from CO2 per encounter with the active site of isozyme III, a process that requires scrambling of oxygens in a bicarbonate-enzyme complex and cycling between intermediate complexes. This suggests that the rate of dissociation of H2(18)O (or 18OH-) from isozyme III is comparable to or faster than substrate and product dissociation.

Depletion of 18O from C18O2 in erythrocyte suspensions. The permeability of the erythrocyte membrane to CO2.

The depletion of 18O from CO2, caused by the exchange of oxygen between CO2 and water during the hydration-dehydration cycle, is catalyzed by carbonic anhydrase. This depletion process at chemical equilibrium in the presence of erythrocytes is biphasic, exhibiting a very rapid depletion rate immediately following the addition of cells to an isotonic solution containing 18O-enriched CO2, followed by a much slower depletion rate. It is hypothesized that these depletion characteristics are caused by the diffusion of labeled CO2 into erythrocytes where depletion occurs rapidly due to the large intracellular carbonic anhydrase content. Kinetic equations which describe this hypothesis are solved and a rate constant is obtained which represents the depletion of 18O in CO2 caused by the presence of red cells. These are equilibrium experiments with no net uptake or loss of CO2 in the cells. Consequently, depletion processes are not limited in rate by bicarbonate-chloride exchange or proton distribution across the membrane. The purpose of these measurements is to determine whether the rate of 18O depletion in red cell suspensions is determined by carbonic anhydrase activity in the cell or by the diffusion process by which CO2 enters the cell. This goal is achieved by partially inhibiting carbonic anhydrase with acetazolamide. The rate constant representing 18O depletion caused by the presence of red cells is unchanged, even though up to 90% of carbonic anhydrase is inhibited. From this rate constant the permeability constant of the membrane of rat erythrocytes to CO2 at 25 degrees and pH 7.4 is determined to be (7.6 +/- 1.2) X 10(-3) cm s-1 in the presence of 3.2 mM picrate, a passive anion diffusion inhibitor intended to block HCO3 -flux across the membrane. Using no picrate and allowing HCO3-flux to introduce an error in the measurements, the permeability constant is (1.6 +/- 0.4) X 10(-2) cm s-1. The permeability constants measured by this technique include the diffusion barrier to CO2 not only of the red cell membrane but also of a portion of the intracellular medium.