Results of a Long-Term International Comparison of Greenhouse Gas and Isotope Measurements at the Global Atmosphere Watch (GAW) Observatory in Alert, Nunavut, Canada
Authors: Worthy Douglas E. J. , Rauh Michele K. , Huang Lin , Vogel Felix R. , Chivulescu Alina , Masarie Kenneth A. , Langenfelds Ray L. , Krummel Paul B. , Allison Colin E. , Crotwell Andrew M. , Madronich Monica , Pétron Gabrielle , Levin Ingeborg , Hammer Samuel , Michel Sylvia , Ramonet Michel , Schmidt Martina , Jordan Armin , Moossen Heiko , Rothe Michael , Keeling Ralph , Morgan Eric J. 
Published: June 2023

Abstract. Since 1999, Environment and Climate Change Canada (ECCC) has been coordinating a multi-laboratory comparison of measurements of long-lived greenhouse gases in whole air samples collected at the Global Atmosphere Watch (GAW) Alert Observatory located in the Canadian high Arctic (82°28' N, 62°30' W). In this paper, we evaluate the measurement agreement of atmospheric CO2, CH4, N2O, SF6, and stable isotopes of CO2 (δ13C, δ18O) between leading laboratories from 7 independent international institutions. The measure of success is linked to target goals for network compatibility outlined by the World Meteorological Organization’s (WMO) GAW greenhouse gas measurement community. Overall, based on ~8000 discrete flask samples, we find that the co-located atmospheric CO2 and CH4 measurement records from Alert by CSIRO, MPI-BGC, SIO, UHEI-IUP, ECCC, and NOAA are generally consistent with the WMO compatibility goals of ±0.1 ppm CO2 and ±2 ppb CH4 over the 17-year period (1999 – 2016), although there are periods where differences exceed target levels and persist as systematic bias for months or years. Consistency with the WMO goals for N2O, SF6, and stable isotopes of CO2 (δ13C, δ18O) has not been demonstrated. Additional analysis of co-located comparison measurements between CSIRO, SIO, and NOAA at other geographical sites suggests that the findings at Alert for CO2, CH4, N2O and δ13C-CO2 could be extended across the CSIRO, SIO, and NOAA observing networks. Two approaches are carried out to determine the level of agreement as a collective for the 7 individual laboratories (1) pooling the differences of individual laboratories over the entire sampling records from a designated reference laboratory and determining the 95th percentile range of these data points and (2) averaging the 2 standard deviations (2-sigma) of the means for all flask samples taken in each individual sampling episode over the entire sampling record. For CO2, from 5691 samples, we derive a measurement agreement level of -0.51 to +0.53 ppm using the 95th percentile range of the differences from NOAA measurements. Similarly, we derive a corresponding value of ± 0.37 ppm using the mean of 2-sigma values from 923 individual weekly sampling episodes. For CO2 isotopes using INSTAAR measurements as a reference, we derive measurement agreement values of -0.09 to +0.07 and ± 0.06 ‰ for δ13C and -0.50 to +0.58 and ± 0.31 ‰ for δ18O, for the 95th percentile ranges and the mean of the 2-sigma values, respectively. For other gases, the corresponding values for both approaches are 4.86 to +6.16 and ± 3.62 ppb for CH4, -0.75 to +1.20 and ± 0.64 ppb for N2O, and -0.14 to +0.09 and ± 0.09 ppt for SF6. These upper and lower limits represent our best estimate of the measurement agreement at the 95 % confidence level for these individual laboratories, providing more confidence for using these datasets in various scientific applications (e.g., long-term trend analysis).