Precise measurements of the total concentration of atmospheric CO2 and 13CO2/12CO2 isotopic ratio using a lead-salt laser diode spectrometer

Rev Sci Instrum. 2008 Apr;79(4):043101. doi: 10.1063/1.2902829.


We have developed a tunable diode laser spectrometer, called SIMCO (spectrometer for isotopic measurements of CO(2)), for determining the concentrations of (12)CO(2) and (13)CO(2) in atmospheric air, from which the total concentration of CO(2) and the isotopic composition (expressed in delta units) delta(13)CO(2) are calculated. The two concentrations are measured using a pair of lines around 2290.1 cm(-1), by fitting a line profile model, taking into account the confinement narrowing effect to achieve a better accuracy. Using the Allan variance, we have demonstrated (for an integration time of 25 s) a precision of 0.1 ppmv for the total CO(2) concentration and of 0.3[per thousand] for delta(13)CO(2). The performances on atmospheric air have been tested during a 3 days campaign by comparing the SIMCO instrument with a gas chromatograph (GC) for the measurement of the total CO(2) concentration and with an isotopic ratio mass spectrometer (MS) for the isotopic composition. The CO(2) concentration measurements of SIMCO are in very good agreement with the GC data with a mean difference of Delta(CO(2))=0.16+/-1.20 ppmv for a comparison period of 45 h and the linearity of the concentration between the two instruments is also very good (slope of correlation: 0.9996+/-0.0003) over the range between 380 and 415 ppmv. For delta(13)CO(2), the comparison with the MS data shows a larger mean difference of Delta(delta(13)CO(2))=(-1.9+/-1.2)[per thousand], which could be partly related to small residual fluctuations of the overall SIMCO instrument response.