Stratospheric CO2 Research Articles

Interannual variations in the Δ(17O) signature of atmospheric CO2 at two mid-latitude sites suggest a close link to stratosphere–troposphere exchange

Abstract. Δ(17O) measurements of atmospheric CO2 have the potential to be a tracer for gross primary production and stratosphere–troposphere mixing. A positive Δ(17O) originates from intrusions of stratospheric CO2, whereas values close to −0.21 ‰ result from the equilibration of CO2 and water, which predominantly happens inside plants. The stratospheric source of CO2 with high Δ(17O) is, however, not well defined in the current models. More, and long-term, atmospheric measurements are needed to improve this. We present records of the Δ(17O) of atmospheric CO2 obtained with laser absorption spectroscopy from Lutjewad in the Netherlands (53°24′ N, 6°21′ E) and Mace Head in Ireland (53°20′ N, 9°54′ W) that cover the period 2017–2022. The records are compared with a 3-D model simulation, and we study potential model improvements. Both records show significant interannual variability of up to 0.3 ‰. The total range covered by smoothed monthly averages from the Lutjewad record is −0.34 ‰ to −0.12 ‰, which is significantly higher than the range of −0.20 ‰ to −0.17 ‰ for the model simulation. The 100 hPa 60–90° N monthly-mean temperature anomaly was used as a proxy to scale stratospheric downwelling in the model. This strongly improves the correlation coefficient of the simulated and observed year-to-year Δ(17O) variations over the period 2019–2021 from 0.40 to 0.82. As the Δ(17O) of atmospheric CO2 seems to be dominated by stratospheric influx, its use as a tracer for stratosphere–troposphere exchange should be further investigated.

Dependency of the impacts of geoengineering on the stratospheric sulfur injection strategy – Part 2: How changes in the hydrological cycle depend on the injection rate and model used

Abstract. This is the second of two papers in which we study the dependency of the impacts of stratospheric sulfur injections on the model and injection strategy used. Here, aerosol optical properties from simulated stratospheric aerosol injections using two aerosol models (modal scheme M7 and sectional scheme SALSA), as described in Part 1 (Laakso et al., 2022), are implemented consistently into the EC-Earth, MPI-ESM and CESM Earth system models (ESMs) to simulate the climate impacts of different injection rates ranging from 2 to 100 Tg(S) yr−1. Two sets of simulations were run with the three ESMs: (1) regression simulations, in which an abrupt change in CO2 concentration or stratospheric aerosols over pre-industrial conditions was applied to quantify global mean fast temperature-independent climate responses and quasi-linear dependence on temperature, and (2) equilibrium simulations, in which radiative forcing of aerosol injections with various magnitudes compensated for the corresponding radiative forcing of CO2 enhancement to study the dependence of precipitation on the injection magnitude. The latter also allow one to explore the regional climatic responses. Large differences in SALSA- and M7-simulated radiative forcing in Part 1 translated into large differences in the estimated surface temperature and precipitation changes in ESM simulations; for example, an injection rate of 20 Tg(S) yr−1 in CESM using M7-simulated aerosols led to only 2.2 K global mean cooling, while EC-Earth–SALSA combination produced a 5.2 K change. In equilibrium simulations, where aerosol injections were utilized to offset the radiative forcing caused by an atmospheric CO2 concentration of 500 ppm, the decrease in global mean precipitation varied among models, ranging from −0.7 % to −2.4 % compared with the pre-industrial climate. These precipitation changes can be explained by the fast precipitation response due to radiation changes caused by the stratospheric aerosols and CO2, as the global mean fast precipitation response is shown to be negatively correlated with global mean atmospheric absorption. Our study shows that estimating the impact of stratospheric aerosol injection on climate is not straightforward. This is because the simulated capability of the sulfate layer to reflect solar radiation and absorb long-wave radiation is sensitive to the injection rate as well as the aerosol model used to simulate the aerosol field. These findings emphasize the necessity for precise simulation of aerosol microphysics to accurately estimate the climate impacts of stratospheric sulfur intervention. This study also reveals gaps in our understanding and uncertainties that still exist related to these controversial techniques.

Comparison of Stratospheric CO2 Measurements by Ground- and Satellite-Based Methods

Comparison of Stratospheric CO2 Measurements by Ground- and Satellite-Based Methods

Retrieval of vertical profiles and tropospheric CO2 columns based on high-resolution FTIR over Hefei, China.

High-resolution solar absorption spectra, observed by ground-based Fourier Transform Infrared spectroscopy (FTIR), are used to retrieve vertical profiles and partial or total column concentrations of many trace gases. In this study, we present the tropospheric CO2 columns retrieved by mid-infrared solar spectra over Hefei, China. To reduce the influence of stratospheric CO2 cross-dependencies on tropospheric CO2, an a posteriori optimization method based on a simple matrix multiplication is used to correct the tropospheric CO2 profiles and columns. The corrected tropospheric CO2 time series show an obvious annual increase and seasonal variation. The tropospheric CO2 annual increase rate is 2.71 ± 0.36 ppm yr-1, with the annual peak value in January, and CO2 decreases to a minimum in August. Further, the corrected tropospheric CO2 from GEOS-Chem simulations are in good agreement with the coincident FTIR data, with a correlation coefficient between GEOS-chem model and FTS of 0.89. The annual increase rate of XCO2 observed from near-infrared solar absorption spectra is in good agreement with the tropospheric CO2 but the annual seasonal amplitude of XCO2 is only about 1/3 of dry-air averaged mole fractions (DMF) of tropospheric CO2. This is mostly attributed to the seasonal variation of CO2 being mainly dominated by sources near the surface.

Wildfire smoke in the lower stratosphere identified by in situ CO observations

Abstract. Wildfires emit large quantities of aerosols and trace gases, which occasionally reach the lower stratosphere. In August 2017, several pyro-cumulonimbus events injected a large amount of smoke into the stratosphere, observed by lidar and satellites. Satellite observations are in general the main method of detecting these events since in situ aircraft- or balloon-based measurements of atmospheric composition at higher altitudes are not made frequently enough. This work presents accidental balloon-borne trace gas observations of wildfire smoke in the lower stratosphere, identified by enhanced CO mole fractions at approximately 13.6 km. In addition to CO mole fractions, CO2 mole fractions and isotopic composition of CO (δ13C and δ18O) have been measured in air samples, from both the wildfire plume and background, collected using an AirCore and a lightweight stratospheric air sampler (LISA) flown on a weather balloon from Sodankylä (4–7 September 2017; 67.37∘ N, 26.63∘ E; 179 m a.m.s.l.), Finland. The greenhouse gas enhancement ratio (ΔCO:ΔCO2) and the isotopic signature based on δ13C(CO) and δ18O(CO) independently identify wildfire emissions as the source of the stratospheric CO enhancement. Back-trajectory analysis was performed with the Chemical Lagrangian Model of the Stratosphere (CLaMS), tracing the smoke's origin to wildfires in British Columbia with an injection date of 12 August 2017. The trajectories are corrected for vertical displacement due to heating of the wildfire aerosols, by observations made by the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument. Knowledge of the age of the smoke allowed for a correction of the enhancement ratio, ΔCO:ΔCO2, for the chemical removal of CO by OH. The stable isotope observations were used to estimate the amount of tropospheric air in the plume at the time of observation to be about 45±21 %. Finally, the plume extended over 1 km in altitude, as inferred from the observations.

Neptune’s carbon monoxide profile and phosphine upper limits from Herschel/SPIRE: Implications for interior structure and formation

On Neptune, carbon monoxide and phosphine are disequilibrium species, and their abundance profiles can provide insights into interior processes and the external space environment. Here we use Herschel/SPIRE (Spectral and Photometric Imaging REceiver) observations from 14.9–51.5 cm-1 to obtain abundances from multiple CO and PH3 spectral features. For CO, we find that nine CO bands can be simultaneously fitted using a step profile with a 0.22 ppm tropospheric abundance, a 1.03 ppm stratospheric abundance, and a step transition pressure of 0.11 bar near the tropopause. This is in broad agreement with previous studies. However, we also find that the CO spectral features could be fitted, to well within measurement errors, with a profile that contains no tropospheric CO for pressure levels deeper than 0.5 bar, which is our preferred interpretation. This differs from previous studies that have assumed CO is well mixed throughout the troposphere, which would require an internal CO source to explain and a high O/H enrichment. Our interpretation removes the requirement for extreme interior O/H enrichment in thermochemical models and can finally reconcile D/H and CO measurements. If true, the lack of lower tropospheric CO would imply a decrease in Neptune’s interior water content, favouring a silicate-rich instead of an ice-rich interior. This would be consistent with a protoplanetary ice source with a similar D/H ratio to the current solar system comet population. The upper tropospheric and stratospheric CO at pressures less than 0.5 bar could then be entirely externally sourced from a giant impact as suggested by Lellouch et al.(2005). We also derive a 3-σ upper limit for PH3 of 1.1 ppb at 0.4–0.8 bar. This is the most stringent upper limit to-date and is entirely consistent with predictions from a simple photochemical model.

Unmasking the negative greenhouse effect over the Antarctic Plateau

A paradoxical negative greenhouse effect has been found over the Antarctic Plateau, indicating that greenhouse gases enhance energy loss to space. Using 13 years of NASA satellite observations, we verify the existence of the negative greenhouse effect and find that the magnitude and sign of the effect varies seasonally and spectrally. A previous explanation attributes this effect solely to stratospheric CO2; however, we surprisingly find that the negative greenhouse effect is predominantly caused by tropospheric water vapor. A recently developed principle-based concept is used to provide a complete account of the Antarctic Plateau’s negative greenhouse effect indicating that it is controlled by the vertical variation of temperature and greenhouse gas absorption. Our findings indicate that unique climatological conditions over the Antarctic Plateau—a strong surface-based temperature inversion and scarcity of free tropospheric water vapor—cause the negative greenhouse effect.

Stratospheric Air Sub-sampler (SAS) and its application to analysis of Δ<sup>17</sup>O(CO<sub>2</sub>) from small air samples collected with an AirCore

Abstract. We present the set-up and a scientific application of the Stratospheric Air Sub-sampler (SAS), a device to collect and to store the vertical profile of air collected with an AirCore (Karion et al., 2010) in numerous sub-samples for later analysis in the laboratory. The SAS described here is a 20 m long 1/4 inch stainless steel tubing that is separated by eleven valves to divide the tubing into 10 identical segments, but it can be easily adapted to collect smaller or larger samples. In the collection phase the SAS is directly connected to the outlet of an optical analyzer that measures the mole fractions of CO2, CH4 and CO from an AirCore sampler. The stratospheric part (or if desired any part of the AirCore air) is then directed through the SAS. When the SAS is filled with the selected air, the valves are closed and the vertical profile is maintained in the different segments of the SAS. The segments can later be analysed to retrieve vertical profiles of other trace gas signatures that require slower instrumentation. As an application, we describe the coupling of the SAS to an analytical system to determine the 17O excess of CO2, which is a tracer for photochemical processing of stratospheric air. For this purpose the analytical system described by Mrozek et al. (2015) was adapted for analysis of air directly from the SAS. The performance of the coupled system is demonstrated for a set of air samples from an AirCore flight in November 2014 near Sodankylä, Finland. The standard error for a 25 mL air sample at stratospheric CO2 mole fraction is 0.56 ‰ (1σ) for δ17O and 0.03 ‰ (1σ) for both δ18O and δ13C. Measured Δ17O(CO2) values show a clear correlation with N2O in agreement with already published data.

Radiocarbon analysis of stratospheric CO<sub>2</sub> retrieved from AirCore sampling

Abstract. Radiocarbon (14C) is an important atmospheric tracer and one of the many used in the understanding of the global carbon budget, which includes the greenhouse gases CO2 and CH4. Measurement of radiocarbon in atmospheric CO2 generally requires the collection of large air samples (a few liters) from which CO2 is extracted and then the concentration of radiocarbon is determined using accelerator mass spectrometry (AMS). However, the regular collection of air samples from the stratosphere, for example using aircraft and balloons, is prohibitively expensive. Here we describe radiocarbon measurements in stratospheric CO2 collected by the AirCore sampling method. AirCore is an innovative atmospheric sampling system, which comprises a long tube descending from a high altitude with one end open and the other closed, and it has been demonstrated to be a reliable, cost-effective sampling system for high-altitude profile (up to ≈ 30 km) measurements of CH4 and CO2. In Europe, AirCore measurements have been being performed on a regular basis near Sodankylä (northern Finland) since September 2013. Here we describe the analysis of samples from two such AirCore flights made there in July 2014, for determining the radiocarbon concentration in stratospheric CO2. The two AirCore profiles were collected on consecutive days. The stratospheric part of the AirCore was divided into six sections, each containing ≈ 35 µg CO2 ( ≈ 9.6 µgC), and stored in a stratospheric air subsampler constructed from 1∕4 in. coiled stainless steel tubing ( ≈ 3 m). A small-volume extraction system was constructed that enabled > 99.5 % CO2 extraction from the stratospheric air samples. Additionally, a new small-volume high-efficiency graphitization system was constructed for graphitization of these extracted CO2 samples, which were measured at the Groningen AMS facility. Since the stratospheric samples were very similar in mass, reference samples were also prepared in the same mass range for calibration and contamination correction purposes. The results show that the Δ14CO2 values from tropopause up to about 19(±1) km for the sample collected on 15 July was 18 ± 6 ‰ (samples 1–4), very similar to the current tropospheric value. On the other hand, Δ14CO2 values from tropopause up to about 18(±1) km for the sample collected on 16 July (samples 1–4) showed a large gradient from −62 to 21 ‰. The next sample in the profile, corresponding to about 18(±1)–22(±2) km (one sample from each profile), shows slight enrichment of 80 ± 20 ‰. The last section from both profiles, containing air from the upper stratosphere, was contaminated with pre-fill air.

Continuous-flow IRMS technique for determining the <sup>17</sup>O excess of CO<sub>2</sub> using complete oxygen isotope exchange with cerium oxide

Abstract. This paper presents an analytical system for analysis of all single substituted isotopologues (12C16O17O, 12C16O18O, 13C16O16O) in nanomolar quantities of CO2 extracted from stratospheric air samples. CO2 is separated from bulk air by gas chromatography and CO2 isotope ratio measurements (ion masses 45 / 44 and 46 / 44) are performed using isotope ratio mass spectrometry (IRMS). The 17O excess (Δ17O) is derived from isotope measurements on two different CO2 aliquots: unmodified CO2 and CO2 after complete oxygen isotope exchange with cerium oxide (CeO2) at 700 °C. Thus, a single measurement of Δ17O requires two injections of 1 mL of air with a CO2 mole fraction of 390 μmol mol−1 at 293 K and 1 bar pressure (corresponding to 16 nmol CO2 each). The required sample size (including flushing) is 2.7 mL of air. A single analysis (one pair of injections) takes 15 minutes. The analytical system is fully automated for unattended measurements over several days. The standard deviation of the 17O excess analysis is 1.7‰. Multiple measurements on an air sample reduce the measurement uncertainty, as expected for the statistical standard error. Thus, the uncertainty for a group of 10 measurements is 0.58‰ for Δ 17O in 2.5 h of analysis. 100 repeat analyses of one air sample decrease the standard error to 0.20‰. The instrument performance was demonstrated by measuring CO2 on stratospheric air samples obtained during the EU project RECONCILE with the high-altitude aircraft Geophysica. The precision for RECONCILE data is 0.03‰ (1σ) for δ13C, 0.07‰ (1σ) for δ18O and 0.55‰ (1σ) for δ17O for a sample of 10 measurements. This is sufficient to examine stratospheric enrichments, which at altitude 33 km go up to 12‰ for δ17O and up to 8‰ for δ18O with respect to tropospheric CO2 : δ17O ~ 21‰ Vienna Standard Mean Ocean Water (VSMOW), δ18O ~ 41‰ VSMOW (Lämmerzahl et al., 2002). The samples measured with our analytical technique agree with available data for stratospheric CO2.

On the Δ17O budget of atmospheric O2

We modeled the Δ17O of atmospheric O2 using 27 ordinary differential equations comprising a box model composed of the stratosphere, troposphere, geosphere, hydrosphere and biosphere. Results show that 57% of the deficit in 17O in O2 relative to a reference water fractionation line is the result of kinetic isotope fractionation attending the Dole effect, 33% balances the positive Δ17O of O(1D) in the stratosphere, and 10% is from evapotranspiration. The predicted Δ′17O O2 relative to waters is −0.410‰ as measured at the δ18O of air. The value for Δ′17O O2 varies at fixed δ18O with the concentration of atmospheric CO2, gross primary production, and net primary production as well as with reaction rates in the stratosphere. Our model prediction is consistent with our measurements of the oxygen isotopic composition of air O2 compared with rocks if rocks define a fractionation line with an intercept in δ′17O=103ln(δ17O/103+1) vs. δ′18O=103ln(δ18O/103+1) space less than SMOW but more positive than some recent measurements imply. The predicted Δ17O is less negative than that obtained from recent measurements of O2 directly against SMOW. Underestimation of Δ′17O O2 can only be ameliorated if the integrated (bulk) Δ′17O for stratospheric CO2 is significantly greater than measurements currently allow. Our results underscore the need for high-precision comparisons of the 17O/16O and 18O/16O ratios of atmospheric O2, VSMOW, and rocks.

AN EXTERNAL ORIGIN FOR CARBON MONOXIDE ON URANUS FROM HERSCHEL /SPIRE?

Previous studies have demonstrated an external source of CO on Jupiter, Saturn, and Neptune. However, it has not been possible to demonstrate this on Uranus because of its low CO abundance, low upper-tropospheric temperatures, and low stratospheric thermal gradient, which make detection very challenging. Here we use 17 Herschel/SPIRE observation sequences spanning 3 yr (2009–2012), which cover 14.6–51.8 cm −1 with a combined integration time of 5 hr. These spectra were originally taken for routine calibration purposes, so were corrected for continuum offsets prior to analysis. The final stacked spectra had an extremely low noise level of 10–50 pW cm −2 sr −1 /cm −1 . Despite this, CO was not observed, but we were able to obtain stringent 3σ upper limits at the 0.1–0.2 bar level of 2.1 ppb for a uniform profile, and 9.4 ppb for a stratosphere-only profile—an order of magnitude improvement over previous studies. Comparison with observed CO fluorescence by Encrenaz et al. suggests the majority of Uranus’ stratospheric CO has an external origin. It thus appears that external supply of oxygen species—via comets, micrometeorites, or dust—is an important process on all giant planets in our solar system. Key word: planets and satellites: atmospheres

Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in (17)O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the (17)O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O((1)D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of (17)O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

Triple oxygen isotope equilibrium fractionation between carbon dioxide and water

The growing number of recent high precision triple oxygen isotope data of water and atmospheric gases requires the reinvestigation of the major isotope fractionation processes between the hydro-, bio- and atmosphere. Here we present the experimental triple oxygen isotope fractionation factor between CO2 gas and water in the temperature range between 2 and 37°C. We have determined the triple oxygen isotope fractionation factor, θ=ln17α/ln18α, for CO2–water equilibrium and found that θCO2–water=0.522±0.002 (t0.95×SEM). No temperature dependence was resolved. Knowledge on the triple oxygen isotope equilibrium fractionation between CO2 and water is crucial for estimating the triple oxygen isotope composition of tropospheric CO2. Model predictions combined with high-precision Δ17O analysis of tropospheric CO2 might reveal new information on biosphere–atmosphere interactions or the influx of anomalous stratospheric CO2.

Revising the retrieval technique of a long-term stratospheric HNO<sub>3</sub> data set: from a constrained matrix inversion to the optimal estimation algorithm

Abstract. The Ground-Based Millimeter-wave Spectrometer (GBMS) was designed and built at the State University of New York at Stony Brook in the early 1990s and since then has carried out many measurement campaigns of stratospheric O3, HNO3, CO and N2O at polar and mid-latitudes. Its HNO3 data set shed light on HNO3 annual cycles over the Antarctic continent and contributed to the validation of both generations of the satellite-based JPL Microwave Limb Sounder (MLS). Following the increasing need for long-term data sets of stratospheric constituents, we resolved to establish a long-term GMBS observation site at the Arctic station of Thule (76.5° N, 68.8° W), Greenland, beginning in January 2009, in order to track the long- and short-term interactions between the changing climate and the seasonal processes tied to the ozone depletion phenomenon. Furthermore, we updated the retrieval algorithm adapting the Optimal Estimation (OE) method to GBMS spectral data in order to conform to the standard of the Network for the Detection of Atmospheric Composition Change (NDACC) microwave group, and to provide our retrievals with a set of averaging kernels that allow more straightforward comparisons with other data sets. The new OE algorithm was applied to GBMS HNO3 data sets from 1993 South Pole observations to date, in order to produce HNO3 version 2 (v2) profiles. A sample of results obtained at Antarctic latitudes in fall and winter and at mid-latitudes is shown here. In most conditions, v2 inversions show a sensitivity (i.e., sum of column elements of the averaging kernel matrix) of 100 ± 20 % from 20 to 45 km altitude, with somewhat worse (better) sensitivity in the Antarctic winter lower (upper) stratosphere. The 1σ uncertainty on HNO3 v2 mixing ratio vertical profiles depends on altitude and is estimated at ~15 % or 0.3 ppbv, whichever is larger. Comparisons of v2 with former (v1) GBMS HNO3 vertical profiles, obtained employing the constrained matrix inversion method, show that v1 and v2 profiles are overall consistent. The main difference is at the HNO3 mixing ratio maximum in the 20–25 km altitude range, which is smaller in v2 than v1 profiles by up to 2 ppbv at mid-latitudes and during the Antarctic fall. This difference suggests a better agreement of GBMS HNO3 v2 profiles with both UARS/ and EOS Aura/MLS HNO3 data than previous v1 profiles.

Stratospheric ozone during the Last Glacial Maximum

Stratospheric ozone during the Last Glacial Maximum (LGM) is investigated in on‐line simulations with the GISS Global Climate/Middle Atmosphere Model 3. LGM boundary conditions and atmospheric concentrations are employed in three simulations: without interactive ozone, with ozone photochemistry appropriate for that time period and with the LGM climate but current atmospheric composition for chemistry. Results show stratospheric ozone increased during the LGM due to reduced NOy and chlorine, while warmer stratospheric temperatures (from reduced stratospheric CO2) decrease ozone with current photochemistry. The stratospheric residual circulation intensified in the lowermost stratosphere, increasing stratosphere/troposphere exchange at higher latitudes, although for most of the middle atmosphere the circulation decreased; the age of air in the Middle Atmosphere increased by up to one year. Compared with the vastly different LGM conditions, increase in stratospheric ozone of 2% by mass had little effect on atmospheric dynamics, and increased the global radiation balance by <0.1 Wm−2.

Long-term observation of mass-independent oxygen isotope anomaly in stratospheric CO<sub>2</sub>

Abstract. Stratospheric and upper tropospheric air samples were collected during 1994–2004 over Sanriku, Japan and in 1997 over Kiruna, Sweden. Using these archived air samples, we determined the triple oxygen-isotope composition of stratospheric CO2 and the N2O mixing ratio. The maximum Δ17OCO2 value of +12.2‰, resembling that observed previously in the mesosphere at 60 km height, was found in the middle stratosphere over Kiruna at 25.6 km height, suggesting that upper stratospheric and mesospheric air descended to the middle stratosphere through strong downward advection. A least-squares regression analysis of our observations on a δ18OCO2−δ17OCO2 plot (r2>0.95) shows a slope of 1.63±pm0.10, which is similar to the reported value of 1.71±0.06, thereby confirming the linearity of three isotope correlation with the slope of 1.6–1.7 in the mid-latitude lower and middle stratosphere. The slope decrease with increasing altitude and a curvy trend in three-isotope correlation reported from previous studies were not statistically significant. Using negative linear correlations of Δ17OCO2 and δ18OCO2 with the N2O mixing ratio, we quantified triple oxygen-isotope fluxes of CO2 to the troposphere as +48‰ GtC/yr (Δ17OCO2) and +38‰ GtC/yr (δ18OCO2) with ~30% uncertainty. Comparing recent model results and observations, underestimation of the three isotope slope and the maximum Δ17OCO2 value in the model were clarified, suggesting a smaller O2 photolysis contribution than that of the model. Simultaneous observations of δ18OCO2, δ17OCO2, and N2O mixing ratios can elucidate triple oxygen isotopes in CO2 and clarify complex interactions among physical, chemical, and photochemical processes occurring in the middle atmosphere.

On the attribution of stratospheric ozone and temperature changes to changes in ozone-depleting substances and well-mixed greenhouse gases

Abstract. The vertical profile of global-mean stratospheric temperature changes has traditionally represented an important diagnostic for the attribution of the cooling effects of stratospheric ozone depletion and CO2 increases. However, CO2-induced cooling alters ozone abundance by perturbing ozone chemistry, thereby coupling the stratospheric ozone and temperature responses to changes in CO2 and ozone-depleting substances (ODSs). Here we untangle the ozone-temperature coupling and show that the attribution of global-mean stratospheric temperature changes to CO2 and ODS changes (which are the true anthropogenic forcing agents) can be quite different from the traditional attribution to CO2 and ozone changes. The significance of these effects is quantified empirically using simulations from a three-dimensional chemistry-climate model. The results confirm the essential validity of the traditional approach in attributing changes during the past period of rapid ODS increases, although we find that about 10% of the upper stratospheric ozone decrease from ODS increases over the period 1975–1995 was offset by the increase in CO2, and the CO2-induced cooling in the upper stratosphere has been somewhat overestimated. When considering ozone recovery, however, the ozone-temperature coupling is a first-order effect; fully 2/5 of the upper stratospheric ozone increase projected to occur from 2010–2040 is attributable to CO2 increases. Thus, it has now become necessary to base attribution of global-mean stratospheric temperature changes on CO2 and ODS changes rather than on CO2 and ozone changes.

A general algorithm for the 17O abundance correction to 13C/ 12C determinations from CO 2 isotopologue measurements, including CO 2 characterised by ‘mass-independent’ oxygen isotope distributions

It is widely recognised that a significant limitation to the ultimate precision of carbon stable isotope ratio measurements, as obtained from dual-inlet mass spectrometric measurements of CO 2 isotopologue ion abundances at m/ z 44, 45, and 46, is the correction for interference from 17O-bearing molecular ions. Two long-established, alternative procedures for determining the magnitude of this correction are in widespread use (although only one has IAEA approval); their differences lead to small but potentially significant discrepancies in the magnitude of the resulting correction. Furthermore, neither approach was designed to accommodate oxygen three-isotope distributions which do not conform to terrestrial mass-dependent behaviour. Stratospheric CO 2, for example, contains a strongly ‘mass-independent’ oxygen isotope composition. A new strategy for determining the 17O-bearing ion correction is presented, for application where the oxygen three-isotope characteristics of the analyte CO 2 are accurately known (or assigned) in terms of the slope λ of the three-isotope fractionation line and the ordinate axis intercept 10 3 ln(1 + k) on a 10 3 ln(1 + δ 17O) versus 10 3 ln(1 + δ 18O) plot. At the heart of the approach is the relationship between 17R, which is the 17O/ 16O ratio of the sample CO 2, and other assigned or empirically determined parameters needed for the δ 13C evaluation: 2 18 R ref 17 R ( 1 + k ) 17 R ref 1 λ - 3 ( 17 R ) 2 + 2 17 R 45 R - 46 R = 0 With 45R and 46R as the respective 45/44 and 46/44 ion abundance ratios of the sample, as obtained by measurement of δ 45(CO 2) and δ 46(CO 2) values reported relative to a reference material (usually VPDB-CO 2), and 17R ref and 18R ref being the respective 17O/ 16O and 18O/ 16O ratios in the same reference material, 17R can readily be obtained by numerical methods, for given λ and k values. The correction procedure involves no approximations, in principle, and is equally applicable to CO 2 of terrestrial, mass-dependent oxygen isotopic composition, as well as to more ‘exotic’ sources. Besides isotopic characterisation of stratospheric CO 2, potential applications include high precision δ 13C measurements of CO 2 derived from the oxidation of tropospheric CO (also characterised by significantly ‘mass-independent’ oxygen isotopic composition); high precision isotopic monitoring of atmospheric CO 2; the metrology of carbonate isotopic reference materials; and the isotopic characterisation of CO 2 which has been equilibrated with waters artificially ‘labelled’ with known enrichments of 17O and 18O.

Investigations of the photochemical isotope equilibrium between O<sub>2</sub>, CO<sub>2</sub> and O<sub>3</sub>

Abstract. Contrary to tropospheric CO2 whose oxygen isotopic composition follows a standard mass dependent relationship, i.e. δ17O~0.5δ18O, stratospheric CO2 is preferentially enriched in 17O, leading to a strikingly different relation: δ17O~1.7δ18O. It has been shown repeatedly that the isotope anomaly is inherited from O3 via photolytically produced O(1D) that undergoes isotope exchange with CO2 and the anomaly may well serve as a tracer of stratospheric chemistry if details of the exchange mechanism are understood. We have studied the photochemical isotope equilibrium in UV-irradiated O2-CO2 and O3-CO2 mixtures to quantify the transfer of the anomaly from O3 to CO2 at room temperature. By following the time evolution of the oxygen isotopic compositions of CO2 and O2 under varying initial isotopic compositions of both, O2/O3 and CO2, the isotope equilibria between the two reservoirs were determined. A very strong dependence of the isotope equilibrium on the O2/CO2-ratio was established. Equilibrium enrichments of 17O and 18O in CO2 relative to O2 diminish with increasing CO2 content, and this reduction in the equilibrium enrichments does not follow a standard mass dependent relation. When molecular oxygen exceeds the amount of CO2 by a factor of about 20, 17O and 18O in equilibrated CO2 are enriched by (142±4)‰ and (146±4)‰, respectively, at room temperature and at a pressure of 225 hPa, independent of the initial isotopic compositions of CO2 and O2 or O3. From these findings we derive a simple and general relation between the starting isotopic compositions and amounts of O2 and CO2 and the observed slope in a three oxygen isotope diagram. Predictions from this relation are compared with published laboratory and atmospheric data.