Botanical characterization and authentication of lavender essential oil using its volatile organic compounds and compound-specific carbon and hydrogen isotope ratio analysis

The determination of authenticity and provenance is one of the main issues in high-value natural products such as lavender (L. angustifolia) essential oil. Due to their high value, natural products are often totally or partially substituted with cheaper alternatives. Therefore, it is necessary to accurately characterize the composition of lavender essential oil and its related species, particularly lavandin (L. intermedia) essential oil, which is frequently used as an adulterant. In this study, we analyzed the most distinctive volatile organic compounds (VOCs) and their relative compound-specific stable carbon and hydrogen (δ13C and δ2H) isotope ratios in lavender, lavandin, and commercial lavender essential oil samples using fast GC-MS/MS and GC-IRMS methods and sparse Partial Least Square Discriminant Analysis (sPLS-DA) to classify and verify their botanical origin. For the first time, concentration ranges for 79 VOCs and the δ13C and δ2H values in 32 VOCs were used to characterize lavender essential oils. sPLS-DA models with either VOCs, δ13C and δ2H, or in combination successfully classify lavender and lavandin with 100% accuracy. VOCs such as camphor, borneol, eucalyptol, α-bisabolol, and α-pinene were found to be the most important variables for differentiating lavender oil from lavandin. Similarly, δ13C in camphor, eucalyptol, trans-β-ocimene and 3-octanone, and δ2H in α-terpineol and trans-β-ocimene and 3-octanone also differentiated lavender and lavandin oil. In addition, we demonstrated that compound-specific δ13C and δ2H detected the adulteration of natural lavender or lavandin oil if more than 15% of linalool, linalyl acetate, eucalyptol, and α-terpineol were of synthetic origin. These preliminary results with sPLS-DA models suggest that VOCs and compound-specific δ13C and δ2H can be a promising tool for the botanical classification of lavender essential oil and the detection of possible adulteration with synthetic compounds