Evaluation of a cavity ring-down spectrometer for in situ observations of 13CO2

With the emergence of wide-spread application of new optical techniques to monitor δ13C in atmospheric CO2 there is a growing need to ensure well-calibrated measurements. We characterized one commonly available instrument, a cavity ring-down spectrometer (CRDS) system used for continuous in situ monitoring of atmospheric 13CO2. We found no dependency of δ13C on the CO2 concentration in the range of 303–437 ppm. We designed a calibration scheme according to the diagnosed instrumental drifts and established a quality assurance protocol. We find that the repeatability (1-σ) of measurements is 0.25‰ for 10 min and 0.15‰ for 20 min integrated averages, respectively. Due to a spectral overlap, our instrument displays a cross-sensitivity to CH4 of 0.42 ± 0.024‰ ppm 1. Our ongoing target measurements yield standard deviations of δ13C from 0.22‰ to 0.28‰ for 10 min averages. We furthermore estimate the reproducibility of our system for ambient air samples from weekly measurements of a long-term target gas to be 0.18‰. We find only a minuscule offset of 0.002 ± 0.025‰ between the CRDS and Environment Canada's isotope ratio mass spectrometer (IRMS) results for four target gases used over the course of one year.