Simultaneous evaluation of the enantiomeric and carbon isotopic ratios of Cannabis sativa L. essential oils by multidimensional gas chromatography

Recent times have witnessed an upsurge of interest in hemp and hemp-derived products, as driven by the scientific findings specific to the pharmacological properties of Cannabis sativa L. and its constituents. There has been evidence that the terpene profile, along with the cannabinoid content, produces in humans the effects associated with different strains, beyond fragrance perception. A great deal of effort has been put into developing analytical approaches to strengthen the scientific knowledge on cannabis essential oil composition and provide effective tools for ascertaining the authenticity of commercial cannabis samples. For this concern, enantio-selective-GC-C-IRMS has proven to be effective for assessing the ranges characteristic of the genuine samples and detecting any fraudulent additions. This research aimed at providing for the first time the enantiomeric and isotopic ratios of target terpenes in cannabis essential oils, obtained from microwave-assisted hydro-distillation from the fresh and dried inflorescences of different cannabis varieties. Implementing multidimensional gas chromatography separation was mandatory prior to detection, in order to obtain accurate δ13C values and enantiomeric data from completely separated peaks. For this purpose, a heart-cut method was developed, based on the coupling of an apolar first dimension column to a secondary chiral cyclodextrin-based stationary phase. Afterwards, the data gathered from enantio-selective-MDGC-C-IRMS/qMS analysis of a set of genuine samples were used to evaluate the quality of nineteen commercial cannabis essential oils purchased from local stores. Remarkably, the data in some cases evidenced enantiomeric ratios and δ13C values outside the typical ranges of genuine oils. Such findings suggest the usefulness of the method developed to ascertain the genuineness and quality of cannabis essential oils. Graphical abstract: [Figure not available: see fulltext.]