Abstract
We present here, an experimental set-up developed for the first time in India for the determination of mixing ratio and carbon isotopic ratio of air-CO2. The set-up includes traps for collection and extraction of CO2 from air samples using cryogenic procedures, followed by the measurement of CO2 mixing ratio using an MKS Baratron gauge and analysis of isotopic ratios using the dual inlet peripheral of a high sensitivity isotope ratio mass spectrometer (IRMS) MAT 253. The internal reproducibility (precision) for the δ 13C measurement is established based on repeat analyses of CO2±0.03‰. The set-up is calibrated with international carbonate and air-CO2 standards. An in-house air-CO2 mixture, ‘OASIS AIRMIX’ is prepared mixing CO2 from a high purity cylinder with O2 and N2 and an aliquot of this mixture is routinely analyzed together with the air samples. The external reproducibility for the measurement of the CO2 mixing ratio and carbon isotopic ratios are ±7 (n = 169) $\upmu $ mol·mol − 1 and ±0.05 (n = 169) ‰ based on the mean of the difference between two aliquots of reference air mixture analyzed during daily operation carried out during November 2009–December 2011. The correction due to the isobaric interference of N2O on air-CO2 samples is determined separately by analyzing mixture of CO2 (of known isotopic composition) and N2O in varying proportions. A +0.2‰ correction in the δ 13C value for a N2O concentration of 329 ppb is determined. As an application, we present results from an experiment conducted during solar eclipse of 2010. The isotopic ratio in CO2 and the carbon dioxide mixing ratio in the air samples collected during the event are different from neighbouring samples, suggesting the role of atmospheric inversion in trapping the emitted CO2 from the urban atmosphere during the eclipse.
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