Tonka bean extract, prepared from Tonka beans, is mainly composed of Coumarin. However, due to alternative industrial procedure of production, different solvents and mixtures of solvents were tested for extraction. Investigation using HPLC-DAD-MS indicates influence of extraction procedure on compositions of main constituents. New polyphenols structures have also been found in extracts and improve the chemical analysis knowledge of these products. Waxes compositions using fatty acids methyl esters gas chromatography analysis have been determined and indicate important amounts of behenic and lignoceric acids. High polar constituents (sugars) were also pointed out with trimethyl silanization. As synthetic Coumarin addition represents the main adulteration, isotopic values of Tonka coumarin, isolated by crystallization, have also been determined using an elemental analyzer connected to an isotope ratio mass spectrometer (EA-IRMS). The delta 13C values of authentic coumarin range from - 32.88 to - 31.38%o for delta 13C, between - 113%o and - 83%o for delta 2H, and between 23.0 and 28.0%o for delta 18O. No isotopic effect was observed with different solvents extraction procedures, indicating that IRMS investigation of Coumarin is a powerful tool applied for naturalness control.

Authentic Lavandula angustifolia (lavender) essential oil samples (n = 41) were procured from six producing countries. Essential oils were analyzed to determine physical properties and to determine profiles and related data by GC/MS, GC/FID, enantioselective GC, and GC/IRMS. The current study identified 43 volatile compounds that were detected in all authentic lavender samples (n = 41), and which can be considered authentic markers. Enantiomeric ranges for 15 volatile compounds and stable isotope ranges for four prominent compounds were determined in authentic lavender. Authentic samples and associated data were used to assess the quality of commercially available lavender essential oil samples (n = 12). 75% of the commercial samples studied were adulterated,and 17 volatile compounds were detected in these samples which can be considered markers for adulteration. This study establishes the utility and importance of using a multifaceted analytical approach to differentiate quality and determine authenticity of lavender essential oil.

Natural plant extracts are primarily used as raw materials in the cosmetic and perfumery industry. However, adulterations with petrochemical products are occurring in the market, leading to non-100% natural products. Several analytical techniques such as impurity detection or enantioselective ratio assessments have been previously described as good indicators to detect any addition of synthetic products, but these techniques are ineffective with novel type of synthetic pathways such as semisynthesis. In order to improve authentication, development of advanced analytical strategies such as δ18O stable isotopic ratios assessment was tested on spearmint, cinnamon and bitter almond essential oils major metabolites (carvone, (E)-cinnamaldehyde, and benzaldehyde). Natural δ18O mean values (δ18OCarvone = 18.4‰; δ18OCinnamaldehyde = 13.9‰; δ18OBenzaldehyde = 16.5‰) were found to be higher than semisynthetic origin for the 3 studied molecules (δ18OCarvone = 9.2‰; δ18OCinnamaldehyde = 8.8‰; δ18OBenzaldehyde = 10.9‰). These measurements proved to be efficient to discriminate natural and semisynthetic origins of these components and therefore potentially lead to a novel way to authenticate natural products.

Protein separation can be achieved with different modes of capillary electrophoresis, such as with capillary gel electroporesis (CGE) or with capillary zone electrophoresis (CZE). CZE protein mapping of peanut extract was approached in four different ways, combining neutral-coated or multilayer-coated capillaries with pHs well over or under the isoelectric point range of the proteins of interest. At acidic pHs, the mobility ranges of the major peanut allergens Ara h1, Ara h2, Ara h3, and Ara h6 were identified. Although the pH is a major factor in CZE separation, buffers with different compositions but with the same pH and ionic strength showed significantly different resolutions. Different components of the electrolyte were studied in a multifactorial design of experiment. CE-SDS and CZE proved to be suitable for protein mapping and we were able to distinguish different batches of peanut extract and burned peanut extract.

Pure and natural essential oils of Allium species are primarily used in the food industry, but due to their low yield, production quantities can be difficult to achieve and thus can be highly expensive. Due to these problems, adulterations are a reality in this field. The purpose of this research is to develop a multi element stable isotope analysis methodology for authentication of the essential oils of leek, onion, shallot, and chive. Naturalness of these essential oils was achieved by assessment of compound specific δ13C and δ34S: an addition of 5% of synthetic compound can be detected. Chemometric models were undertaken to assess purity by distinction of the Allium samples according to their species origin using bulk stable and compound specific δ13C, δ2H, δ34S, and compositions of their major metabolites dipropyl disulfide, dipropyl trisulfide, methyl propyl disulfide, and methyl propyl trisulfide.

Neroli essential oil (EO), extracted from bitter orange blossoms, is one of the most expensive natural products on the market due to its poor yield and its use in fragrance compositions, such as cologne. Multiple adulterations of neroli EO are found on the market, and several authentication strategies, such as enantioselective gas chromatography (GC) and isotope ratio mass spectrometry (IRMS), have been developed in the last few years. However, neroli EO adulteration is becoming increasingly sophisticated, and analytical improvements are needed to increase precision. Enantiomeric and compound-specific isotopic profiling of numerous metabolites using multidimensional GC and GC-C/P-IRMS was carried out. These analyses proved to be efficient for geographical tracing, especially to distinguish neroli EO of Egyptian origin. In addition, δ2H values and enantioselective ratios can identify an addition of 10% of petitgrain EO. These results demonstrate that enantioselective and stable isotopic metabolite fingerprint determination is currently a necessity to control EOs.

The essential oil of wintergreen, which is extracted by steam distillation from Gaultheria genus leaves, is mainly used in aromatherapy. However, due to its adulteration easiness with synthetic material, it is necessary to control samples naturalness with accuracy. The purpose of this work was to develop a methodology to authenticate the essential oil of wintergreen. Wintergreen essential oil is composed of more than 99% methyl salicylate. This aromatic ester can be easily synthesized and used to adulterate wintergreen essential oil. Authentic wintergreen essential oil can be distinguished from adulterated oils by examining their compositions. The detection of methyl salicylate synthetic marker compounds (methyl 4-hydroxybenzoate, dimethyl 4-hydroxyisophthalate or dimethyl 2-hydroxyisophthalate) or the absence of several naturally occurring minor secondary metabolites (ethyl salicylate and vitispirane) contribute to the authentication. Isotopic values of bulk wintergreen essential oil have also been determined using an isotope ratio mass spectrometer (IRMS): the δ13C values of authentic samples range from −36.78 to −33.36‰, the δ2H values range from −173 to −115‰ and the δ18O values range from −1.3 to 5.7‰. However, these analytical methods cannot account for the natural variability in the essential oils. To determine the boundaries of the natural isotopic values, 14C radioactive isotope activity assessment was undertaken, which allows for the determination of the genuineness of samples that are not assessed using multistable isotope approaches. Additional studies evaluating 14C activity of a noncompliant sample using IRMS identified a 14C-labeled synthetic methyl salicylate adulteration.