Estimating uncertainty of the WMO mole fraction scale for carbon dioxide in air

Abstract

The current WMO CO 2 Mole Fraction Scale consists of a set of 15 CO 2‐in‐air primary standard calibration gases ranging in CO 2 mole fraction from 250 to 520 μmol mol−1. Since the WMO CO 2 Expert Group transferred responsibility for maintaining the WMO Scale from the Scripps Institution of Oceanography (SIO) to the Climate Monitoring and Diagnostics Laboratory (CMDL) in 1995, the 15 WMO primary standards have been calibrated, first at SIO and then at regular intervals, between 1 and 2 years, by the CMDL manometric system. The uncertainty of the 15 primary standards was estimated to be 0.069 μmol mol−1(one‐sigma) in the absolute sense. Manometric calibrations results indicate that there is no evidence of overall drift of the Primaries from 1996 to 2004. In order to lengthen the useful life of the Primary standards, CMDL has always transferred the scale via NDIR analyzers to the secondary standards. The uncertainties arising from the analyzer random error and the propagation error due to the uncertainty of the reference gas mole fraction are discussed. Precision of NDIR transfer calibrations was about 0.014 μmol mol−1 from 1979 to present. Propagation of the uncertainty was calculated theoretically. In the case of interpolation the propagation error was estimated to be between 0.06 and 0.07 μmol mol−1 when the Primaries were used as the reference gases via NDIR transfer calibrations. The CMDL secondary standard calibrations are transferred via NDIR analyzers to the working standards, which are used routinely for measuring atmospheric CO 2 mole fraction in the WMO Global Atmosphere Watch monitoring program. The uncertainty of the working standards was estimated to be 0.071 μmol mol−1 in the one‐sigma absolute scale. Consistency among the working standards is determined by the random errors of downward transfer calibrations at each level and is about 0.02 μmol mol−1. For comparison with an independent absolute scale, the five gravimetric standards from the National Institute for the Environmental Studies (NIES) in Tsukuba, Japan, ranging in CO 2 mole fraction from 350 to 390 μmol mol−1 have been calibrated relative to the CMDL secondary standards. The average and standard deviation of the differences between the NIES gravimetric and CMDL analyzed CO 2 mole fraction are 0.004 ± 0.03 μmol mol−1.