Natural isotope fractionation in the discrimination of sugar origins

More than 500 carbohydrate samples have been characterised by hydrogen, carbon and oxygen isotopic parameters measured on ethanol and water resulting from controlled fermentation. Different chemical states of the carbohydrate pool have been considered: polysaccharides from cereals, tubers and leguminosae (maize, sorghum, rice, wheat, barley, potato, bean), glucose, fructose and sucrose from fruits (pineapple, citrus, apple, soft fruits), sucrose from sugar plants (beet, cane). The overall carbon-13 content of ethanol and the deuterium and oxygen-18 contents of water before fermentation were determined by mass spectrometry of isotope ratios whereas the investigation of site-specific natural isotope fractionation by deuterium NMR has provided access to the deuterium contents in the methyl (I) and methylene (II) sites of ethanol. The results have been analysed in the multidimensional space of these isotopic variables. Hierarchical clustering, principal component and discriminant analyses have been performed. Among fruits, for example, the pineapple group exhibits a 100% discrimination with respect to the apple and citrus groups which are themselves well distinguished. A still higher discrimination is reached between the three groups, citrus, cane and beet, and the addition of 10% exogenous cane or beet sucrose to citrus juice is unambiguously detected.