Comparison of various detection limit estimates for volatile sulphur compounds by gas chromatography with pulsed flame photometric detection

This paper addresses the variations that presently exist regarding the definition, determination, and reporting of detection limits for volatile sulphur compounds by gas chromatography with pulsed flame photometric detection (GC-PFPD). Gas standards containing hydrogen sulphide (H2S), carbonyl sulphide (COS), sulphur dioxide (SO2), methyl mercaptan (CH3SH), dimethyl sulphide (DMS), carbon disulphide (CS2), and dimethyl disulphide (DMDS) in concentrations varying from 0.36 ppb (v/v) up to 1.5 ppm (v/v) in nitrogen were prepared with permeation tubes and introduced in the gas chromatograph using a 0.25-ml gas sampling loop. After measuring the PFPD response versus concentration, the method detection limit (MDL), the Hubaux–Vos detection limit (xD), the absolute instrument sensitivity (AIS), and the sulphur detectivity (Ds) were determined for each sulphur compound. The results show that the MDL determined by the US Environmental Protection Agency procedure consistently underestimates the minimum concentrations of volatile sulphur compounds that can be practically distinguished from the background noise with the PFPD. The Hubaux–Vos detection limits and the AIS values are several times higher than the MDL, and provide more conservative estimates of the lowest concentrations that can be reliably detected. Sulphur detectivities are well correlated with AIS values but only poorly correlated with MDL values. The AIS is recommended as a reliable and cost-effective measure of detection limit for volatile sulphur compounds by GC-PFPD, since the AIS is easier and faster to determine than the MDL and the Hubaux–Vos detection limit. In addition, this study confirmed that the PFPD response is nearly quadratic with respect to concentration for all volatile sulphur compounds.