Validation and Comparison of Calibration Techniques for Measurements of Carbon Dioxide in Atmospheric Air Standards

Abstract

The increase in the concentration of carbon dioxide (CO2) in the atmosphere has led the scientific community to investigate the adverse effects on humanity and nature, including the greenhouse effect, which contributes to global warming and can lead to climate change, besides the risks associated with human health. Due to the importance of metrological issues in the current scenario, the Laboratory of Gas Analysis (Lanag) of the National Institute of Metrology, Quality and Technology (Inmetro) is developing the methodology of preparation of such primary standard gas mixtures through gravimetry. For the preparation of these standards, an analysis verification step is necessary, carried out by means of an analytical technique of comparison, at low levels of concentration, by cavity ringdown (CRDS) and by gas chromatography using a flame ionization detector coupled to a methaniser catalyst (GC-FIDmeth). This work presents the method validation of both methodologies developed to analyze a range of concentration of atmospheric standards of CO2 at a matrix of synthetic clean dry air (SCDA) by CRDS and GC-FIDmeth, of which the analysis results can compromise the measurements on atmospheric air quality. The objective is to compare results of method validation of both analytical methods for low CO2 concentration through the use of primary reference mixtures developed and also by certified reference material. The validation measurement results were analyzed according to the requirements of ISO 5725: 1994 parts 1 and 2, and the calculation of measurement uncertainty followed the methodology described in ISO 6143:2001, with results showing satisfactory consistent between both selected techniques. According to the work presented here, the obtained validation results for CRDS are better than the GC results, such as the relative uncertainty of samples evaluated for CRDS was 0.4% and 2.7% for GC_FID meth.