Toward continuous monitoring of seawater 13CO2/12CO2 isotope ratio and pCO2: Performance of cavity ringdown spectroscopy and gas matrix effects

Gernot Friedrichs, Julia Bock, Friedrich Temps, Peer Fietzek, Arne Körtzinger, and Douglas W. R. Wallace

Limnol. Oceanogr. Methods 8:539-551 (2010) | DOI: 10.4319/lom.2010.8.539

ABSTRACT: The potential of a continuous wave cavity ringdown spectrometer for monitoring the isotope ratio 13CO2/12CO2 and the partial pressure pCO2 of CO2 dissolved in water was thoroughly analyzed by quantitative measurements. Running calibration gas standards under typical operation conditions, a relative accuracy of Δ(δ13C[CO2]) = ±0.1‰ with 120 min averaging time has been demonstrated. Absolute uncertainties were determined to be Δ(δ13C[CO2]) = ±0.2‰ and Δ(xCO2) = ±0.5 ppmv. No principle problems were encountered when using the instrument in combination with a water-air equilibration setup. By contrast, when performing measurements of CO2 in gas matrices with a composition different from that of ambient air, pressure broadening linewidth effects induced significant errors in both δ13C(CO2) and xCO2 values. These effects, which compromise the accessible accuracy in environmental studies, can be quantitatively taken into account by using a spectroscopically based correction procedure. Relying on linewidth analysis, the instrument was shown to be capable of continuous and simultaneous measurement of δ13C(CO2), pCO2, as well as water content and O2 supersaturation, and thus holds the potential for online monitoring of these quantities aboard research vessels.