Improved CRDS δ13C Stability Through New Calibration Application For CO2 and CH4

Abstract:

Stable carbon isotope ratio measurements of CO2 and CH4 provide valuable insight into global and regional sources and sinks of the two most important greenhouse gasses. Methodologies based on Cavity Ring-Down Spectroscopy (CRDS) have been developed capable of delivering δ13C measurements with a precision greater than 0.12 permil for CO2 and 0.4 permil for CH4 (1 hour window, 5 minute average). Here we present a method to further improve this measurement’s stability. We have developed a two point calibration method which corrects for δ13C drift due to a dependance on carbon species concentration. This method calibrates for both carbon species concentration as well as δ13C. We go on to show that this added stability is especially valuable when using carbon isotope data in linear regression models such as Keeling plots, where even small amounts of error can be magnified to give inconclusive results. This method is demonstrated in both laboratory and ambient atmospheric conditions, and we demonstrate how to select the calibration frequency.