Maintaining consistent traceability in high precision isotope measurements of {CO 2 :} verifying atmospheric trends of {δ 13 C}

Abstract

Abstract. Maintaining consistent traceability of high precision measurements of CO2 isotopes is critical in being able to observe accurate atmospheric trends of δ13C (CO2). Although a number of laboratories/organizations around the world have been involved in baseline measurements of atmospheric CO2 isotopes for several decades, the reports on their traceability measures are rare. In this paper, a principle and an approach for the traceability maintenance of high precision isotope measurements (δ13C and δ18O) in atmospheric CO2 is described. The uncertainties of the traceability have been estimated based on the history of annual calibrations over the last 10 yr. The overall uncertainties of CO2 isotope measurements for individual ambient samples carried out by our program at Environment Canada are estimated (excluding the uncertainty associated with the sampling). The values are 0.02‰ and 0.05‰ in δ13C and δ18O, respectively, close to the WMO targets for data compatibility. The annual rate of change in δ13C of the primary anchor used in our program (which is the laboratory standard linking ambient measurements back to the primary VPDB scale) is close to zero (−0.0016 ± 0.0012‰ per year) over the period of 10 yr (2001–2011). The average annual decreasing rate of δ13C in air CO2 measurements at Alert over the period from 1999 to 2010 has been confirmed and verified, which is −0.025 ± 0.003‰ per year. The total change of δ13C in the annual mean value during this period is ∼−0.27‰. The concept of "Big Delta" is introduced and its role in maintaining traceability of the isotope measurements is described and discussed extensively. Finally, the challenges and a strategy for maintaining traceability are also discussed and suggested.