N2O influence on isotopic measurements of atmospheric CO2

In spite of extensive efforts, even the most experienced laboratories dealing with isotopic measurements of atmospheric CO2 still suffer from poor inter-laboratory consistency. One of the complicating factors of these isotope measurements is the presence of N2O, giving rise to mass overlap in the isotope ratio mass spectrometer (IRMS). The aim of the experiment reported here has been twofold: first, the re-establishment of the correction for 'mechanical' interference of N2O in the IRMS, along with its variability and drift, and the best way to quantitatively determine the correction factors. Second, an investigation into secondary effects, i.e. the influence of N2O admitted with the CO2 sample on the "cross contamination"' between sample and (pure CO2) working gas. To make the suspected effects better detectable, isotopically enriched CO2 gas with different concentrations of N2O has been measured for the first time. No evidence of secondary effects was observed, from which we conclude that N2O is not a major player in the inter-laboratory consistency problems. Still, we also found that the determination of the 'mechanical' N2O correction needs to be very carefully determined for each individual IRMS, and should be periodically re-determined. We show that the determination of the correction should be performed using CO2/N2O mixtures with concentration ratios around that of the atmosphere, as the extrapolation from pure gas end member behaviour will give erroneous results due to non-linearities. For our IRMS, a VG SIRA series II, we find a correction of 0.23parts per thousand for delta(45)CO(2) and 0.30parts per thousand for delta(46)CO(2) of atmospheric samples, (with 0.85parts per thousand mixing ratio). This implies that the relative ionisation efficiency (E) value associated with this machine is 0.75. Copyright (C) 2004 John Wiley Sons, Ltd.