Maintaining consistent traceability in high-precision isotope measurements of CO2: A way to verify atmospheric trends of δ13°C and δ18O

Abstract

Maintaining consistent traceability of high-precision measurements of CO2 isotopes is critical in order to obtain accurate atmospheric trends of δ13°C and δ18O (in CO2). Although a number of laboratories/organizations around the world have been conducting baseline measurements of atmospheric CO2 isotopes for several decades, reports on the traceability and maintenance are rare. In this paper, a principle and an approach for maintaining consistent traceability in high-precision isotope measurements (δ13°C and δ18O) of atmospheric CO2 are described. The concept of Big Δ is introduced and its role in maintaining traceability of the isotope measurements is described and discussed extensively. The uncertainties of the traceability have been estimated based on annual calibration records over the last 10 yr. The overall uncertainties of CO 2 isotope measurements for individual ambient samples analyzed by the program at Environment Canada have been estimated (excluding these associated with the sampling). The values are 0.02 and 0.05 in δ13°C and δ18O, respectively, which are close to the World Meteorological Organization (WMO) targets for data compatibility. The annual rates of change in δ13°C and δ18O of the primary anchor (which links the flask measurements back to the VPDB-CO2 scale) are close to zero (-0.0016 ± 0.0012, and-0.006 ± 0.003 per year, respectively) over a period of 10 yr (2001-2011). The average annual changes of δ13°C and δ18O in air CO2 at Alert GAW station over the period from 1999 to 2010 have been evaluated and confirmed; they are-0.025 ± 0.003 and 0.000 ± 0.010, respectively. The results are consistent with a continuous contribution of fossil fuel CO2 to the atmosphere, having a trend toward more negative in δ13°C, whereas the lack of change in δ18O likely reflects the influence from the global hydrologic cycle. The total change of δ13°C and δ18O during this period is ∼0.27 and ∼0.00, respectively. Finally, the challenges and recommendations as strategies to maintain a consistent traceability are described. © 2012 Author(s).