Articles | Volume 8, issue 2
Atmos. Meas. Tech., 8, 811–822, 2015
Atmos. Meas. Tech., 8, 811–822, 2015

Research article 18 Feb 2015

Research article | 18 Feb 2015

Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide

D. J. Mrozek1, C. van der Veen1, M. Kliphuis1, J. Kaiser2, A. A. Wiegel3,*, and T. Röckmann1 D. J. Mrozek et al.
  • 1Institute for Marine and Atmospheric Research Utrecht, Utrecht University, Princetonplein 5, 3584 CC Utrecht, the Netherlands
  • 2Centre for Ocean and Atmospheric Sciences, School of Environmental Sciences, University of East Anglia, Norwich Research Park, Norwich, UK
  • 3Department of Chemistry, University of California, Berkeley, CA, USA
  • *now at: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

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.

Short summary
Our analytical system is a promising tool for investigating the triple oxygen isotope composition of CO2 from stratospheric air samples of volumes 100ml and smaller. The method is designed for measuring air samples with CO2 mole fractions between 360 and 400ppm, and it is the first fully automated analytical system that uses CeO2 as the isotope exchange medium.