Evaluation of a cavity ring-down spectrometer for in situ observations of <sup>13</sup>CO<sub>2</sub>

oleh: D. E. J. Worthy, S. Racki, L. Giroux, D. Ernst, L. Huang, F. R. Vogel

Format: Article
Diterbitkan: Copernicus Publications 2013-02-01

Deskripsi

With the emergence of wide-spread application of new optical techniques to monitor &delta;<sup>13</sup>C in atmospheric CO<sub>2</sub> 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 <sup>13</sup>CO<sub>2</sub>. We found no dependency of &delta;<sup>13</sup>C on the CO<sub>2</sub> 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-&sigma;) of measurements is 0.25&permil; for 10 min and 0.15&permil; for 20 min integrated averages, respectively. Due to a spectral overlap, our instrument displays a cross-sensitivity to CH<sub>4</sub> of 0.42 &plusmn; 0.024&permil; ppm<sup>−1</sup>. Our ongoing target measurements yield standard deviations of &delta;<sup>13</sup>C from 0.22&permil; to 0.28&permil; 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&permil;. We find only a minuscule offset of 0.002 &plusmn; 0.025&permil; between the CRDS and Environment Canada's isotope ratio mass spectrometer (IRMS) results for four target gases used over the course of one year.