Intercomparison of two cavity ring-down spectroscopy analyzers for atmospheric 13CO2/12CO2 measurement

Abstract

Isotope ratio infrared spectroscopy (IRIS) permits continuous in situ measurement of CO2 isotopic composition under ambient conditions. Previous studies have mainly focused on single IRIS instrument performance; few studies have considered the comparability among different IRIS instruments. In this study, we carried out laboratory and ambient measurements using two Picarro CO2δ13C analyzers (G1101-i and G2201-i (newer version)) and evaluated their performance and comparability. The best precision was 0.08-0.15‰ for G1101-i and 0.01-0.04‰ for G2201-i. The dependence of δ13C on CO2 concentration was 0.46‰ per 100 ppm and 0.09‰ per 100 ppm, the instrument drift ranged from 0.92-1.09‰ and 0.19-0.37 ‰, and the sensitivity of δ13C to the water vapor mixing ratio was 1.01‰=% H2O and 0.09‰=% H2O for G1101-i and G2201-i, respectively. The accuracy after correction by the two-point mixing ratio gain and offset calibration method ranged from -0.04-0.09‰for G1101-i and -0.13-0.03‰ for G2201-i. The sensitivity of δ13C to the water vapor mixing ratio improved from 1.01‰=% H2O before the upgrade of G1101-i (G1101-i-original) to 0.15‰=% H2O after the upgrade of G1101-i (G1101-i-upgraded). Atmospheric δ13C measured by G1101-i and G2201-i captured the rapid changes in atmospheric δ13C signals on hourly to diurnal cycle scales, with a difference of 0.07±0.24‰ between G1101-i-original and G2201-i and 0.05±0.30‰ between G1101-i-upgraded and G2201-i. A significant linear correlation was observed between the δ13C difference of G1101-i-original and G2201-i and the water vapor concentration, but there was no significant correlation between the δ13C difference of G1101-i-upgraded and G2201-i and the water vapor concentration. The difference in the Keeling intercept values decreased from 1.24‰ between G1101-i-original and G2201-i to 0.36‰ between G1101-i-upgraded and G2201-i, which indicates the importance of consistency among different IRIS instruments.