Simultaneous measurement of greenhouse gases (CH4, CO2 and N2O) at atmospheric levels using a gas chromatography system

Abstract. This article presents a simple method for determining greenhouse gases (CH₄, CO₂, N₂O) at ambient atmospheric levels using a chromatographic system. The novelty of the presented method is the application of a Carboxen 1010 PLOT capillary column for separation of trace gases – CH₄, CO₂ and N₂O – from air samples and their detection using a barrier discharge ionisation detector (BID). Simultaneously, a parallel molecular sieve column connected to a thermal conductivity detector (TCD) allowed the determination of CH₄, N₂ and O₂ concentrations from 0.1 to 100 %. The system was equipped with an autosampler transferring the samples without air contamination thanks to a vacuum pump-inert gas flushing option. Method validation was performed using commercial gas standards and undertaking a comparison measurement with a reference method: optical methods applying Picarro isotope and concentration instruments with cavity ring-down spectroscopy for CO₂, CH₄ and N₂O. A three-day continuous measurement series of the lowest GHG concentrations in ambient air and tests of typical vial sample measurements with increased GHG concentrations were performed. The advantage of this method is that the system is easy to set up and allows for simultaneous detection and analysis of the main GHGs in their ambient concentrations using one GC column and one detector, thereby omitting the need for an electron capture detector (ECD) containing radiogenic components for N₂O analysis and a flame ionisation detector (FID) with a methaniser for low-concentration CO₂ samples. The simplification of the system reduces analytical costs, facilitates instrument maintenance and improves measurement robustness.