Reevaluation of the NOAA/CMDL carbon monoxide reference scale and comparisons with CO reference gases at NASA-Langley and the Fraunhofer Institut

The carbon monoxide (CO) reference scale created by the National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostics Laboratory (NOAA/CMDL) is used to quantify measurements of CO in the atmosphere, calibrate standards of other laboratories and to otherwise provide reference gases to the community measuring atmospheric CO. This reference scale was created based upon a set of primary standards prepared by gravimetric methods at CMDL and has been propagated to a set of working standards. In this paper we compare CO mixing ratios assigned to the working standards by three approaches: (1) calibration against the original gravimetric standards, (2) calibration using only working standards as the reference gas, and (3) calibration against three new gravimetric standards prepared to CMDL. The agreement between these values was typically better than 1%. The calibration histories of CMDL working standards are reviewed with respect to expected rates of CO change in the atmosphere. Using a Monte Carlo approach to simulate the effect of drifting standards on calculated mixing ratios, we conclude that the error solely associated with the maintenance of standards will limit the ability to detect small CO changes in the atmosphere. We also report results of intercalibration experiments conducted between CMDL and the Diode Laser Sensor Group (DACOM) at the NASA Langley Research Center (Hampton, Virginia), and CMDL and the Fraunhofer-Institut (Garmisch-Partenkirchen, Germany). Each laboratory calibrated several working standards for CO using their reference gases, and these results were compared to calibrations conducted by CMDL. The intercomparison of eight standards (CO concentrations between approximately 100 and approximately 165 ppb) by CMDL and NASA agreed to better than +/- 2%. The calibration of six standards (CO concentrations between approximately 50 and approximately 210 ppb) by CMDL and the Fraunhofer-Institut agreed to within +/- 2% for four standards, and to within +/- 5% for all six standards.