Development of chromatographic methods by using direct-sampling procedure for the quantification of cyclic and linear volatile methylsiloxanes in biogas as perspective for application in online systems.

By empirically examining the persistent theme, we hope to produce a more complete understanding of methods for determination of volatile methylsiloxanes in biogas stream. Therefore, we made an attempt to investigate a rapid and sensitive method for simultaneous analysis of linear and cyclic volatile methylsiloxanes in sewage biogas in the context of the perspective for application in online systems. The gas chromatographic (GC) parameters were optimised, and sampling of volatile methylsiloxanes from biogas was performed using novel direct sampling procedure with applying of three kinds of liquid-media. Through application of well-established gas chromatography technique coupled with two types of detector – flamed ionisation detector and mass spectrometer detector – we developed the characterisation of the presented methods. Moreover, during the samples preparation the extraction procedure was consistently excluded, as well as the time of analysis was significantly reduced. The analyses were carried out by applying special constructed sampling train where the absorbed VMSs were trapped and analysed directly by GC technique, afterwards. The instrumental analytical protocol was found to yield a linear calibration in the range 0.1–55.13 (µg g^?1) with R² values 0.996 and in the range from 0.1 to 65.17 µg g^?1) with R² values > 0.99 for GC-FID and GC-MS method respectively. In all analysed samples linear and cyclic VMSs were found in sewage gas with quantities exceeding 4.6 mg Nm^?3 and 19.9 mg Nm^?3, respectively Furthermore, estimation of VMSs solvent absorption efficiency was tested and the highest absorption efficiency was obtained when acetone was used as a primary solvent. High range of linearity (0.1–65.17 µg/g), and low values of limit of detection (0.01 µg/g), limit of quantification (0.04 µg/g) clearly indicate that the analysis can be successfully repeated in other independent laboratory. The proposed method creates the real perspective for analyis of VMSs in on-line system.