Development of a quantification method for the analysis of malodorous sulphur compounds in gaseous industrial effluents by solid-phase microextraction and gas chromatography–pulsed flame photometric detection

A quantification method for malodorous sulphur compounds in gaseous industrial effluents using solid-phase microextraction sampling followed by gas chromatography–pulsed flame photometric detection has been developed. A comparative study showed that polydimethylsiloxane–Carboxen fibre led to sufficient sensitivity to achieve the μg m−3 human perception levels of the five analytes studied (hydrogen sulphide, methanethiol, ethanethiol, dimethyl sulphide, dimethyl disulphide). However, this coating is known to suffer from competitive adsorption, which may lead to inaccurate quantification. Therefore, external calibration can only be used under a limited range of concentrations, which were determined from Fick’s diffusion law. This approach was tested on a real gaseous sample and compared with the standard addition method. Good correlations were found for ethanethiol, dimethyl sulphide and dimethyl disulphide. However, for more volatile sulphur compounds (i.e., hydrogen sulphide and methanethiol), the easy-to-use external calibration could not be applied and standard additions had to be performed for accurate quantification.