Ionic liquids as water-compatible GC stationary phases for the analysis of fragrances and essential oils

Fragrances and products deriving from essential oils are often formulated or diluted in aqueous media, usually ethanol/water. Gas chromatography (GC) is the technique of choice to analyze volatiles. However, when using columns coated with conventional stationary phases, its application to aqueous samples often requires time-consuming and/or discriminative sample preparation techniques to extract the target analytes from the aqueous medium, so as to avoid its direct injection. In GC with conventional columns, water produces peak asymmetry, poor sensitivity and efficiency, strong adsorption, stationary phase degradation, and, last but not least, it is not easy to detect reliably when present in high amounts. In 2012, Armstrong’s group introduced new fully water-compatible ionic-liquid (IL)-based GC capillary columns based on phosphonium and imidazolium derivative cations combined with trifluoromethanesulphonate. These columns were recently made available commercially by Supelco, under the trade name Watercol™. These derivatives maintain IL’s unique selectivity and chromatographic properties, and enable water to be used as injection solvent, thus avoiding the sample preparation procedures required by conventional columns. This study reports and critically discusses the results of commercially available water-compatible IL columns for direct analysis of aqueous samples in the fragrance and essential oil fields by GC with thermal conductivity (TCD) and/or flame ionization detectors (FID). The results showed that water-compatible IL-based stationary phases can successfully be adopted for qualitative and quantitative analysis of fragrances and essential oils directly diluted in aqueous solvents. On the other hand, the study also shows that their inertness needs to be further increased and (possibly) the range of operative temperature extended when water is the main solvent of the sample.