Stable isotope analysis of atmospheric CO₂ using a Gasbench II-Cold Trap-IRMS setting

The measurement of the stable carbon and oxygen isotope ratio of (atmospheric) carbon dioxide (CO₂ ) is a useful technique for the investigation and identification of the sources and sinks of the most abundant greenhouse gases by far. For this reason, we are presenting a measuring system here that enables a wide range of users to carry out stable isotope analysis of atmospheric CO₂ using off-the-bench hardware and software.

The fully automated system uses cryogenic and gas chromatographic separation to analyse CO₂ from 12-mL whole air samples and consists of an autosampler, a Gasbench II (GB), a downstream cryo trap and a continuous flow gas interface feeding into a sector field mass spectrometer (GC Pal/GB/Cold Trap/ConFlo IV/DeltaV Plus). The evaluation of the system performance was based on the analysis of samples prepared from eight CO₂ sources (four CO₂ reference gases and four artificial air tanks).

The overall measurement uncertainty (averaged single standard deviation (1σ) of measurement replicates from each CO₂ source) in the determination of the carbon and oxygen isotope ratio was 0.04‰ and 0.09‰ (n = 24). Furthermore, we were able to show that the measurement data also allowed for the quantification of the CO₂ mole fraction, with a precision of 1.2 μmol mol^-1 in the analysis range of 400-500 μmol mol^-1 .

Our protocol provides a detailed description of the measurement set-up and the analysis procedure, how raw data should be evaluated and gives recommendations for sample preparation and sampling to enable a fully automated whole air sample analysis. The quantification limit of CO₂ mole fractions and measurement precision for carbon and oxygen isotope ratios of CO₂ should meet the requirements of a wide range of users.