American Chemical Society, Journal of Natural Products, 6(78), p. 1284-1293, 2015
DOI: 10.1021/acs.jnatprod.5b00093
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The molecular composition of ten Cretaceous and one Eocene ambers from France was analyzed by infrared spectroscopy, solid state 13C nuclear magnetic resonance spectroscopy, and thermochemolysis gas chromatography – mass spectrometry. The terpenoids identified in the samples were used as biomarkers for the botanical origin of the resins. The Cretaceous samples, comprising the so-called Alpine, Anjou, Charentese, Provence, Pyrenean, and Vendean ambers, ranged from the Albian–Cenomanian transition to the Early Santonian (100 to 85 Ma) and correspond to Class Ib resins typical of conifers. The extinct conifer family Cheirolepidiaceae was proposed as the plant source of Pyrenean and brown Charentese ambers. Araucariaceae or Cheirolepidiaceae were the plant sources of the Cenomanian Alpine, Anjou, and yellow Charentese ambers. The Santonian ambers of Provence and Vendée were found to derive from the Cupressaceae. The Eocene Oise amber (ca. 53 Ma) is a Class Ic resin typical of angiosperms, and was produced by a Fabaceae. The evolution of resin sources from the Early Cretaceous to the Eocene periods is discussed. Finally, a possible fingerprint hitherto unveiled is proposed for cheirolepidiaceous resins, defined by the simultaneous presence of phenolic diterpenoids, labdanoic acids, callitrisate structures, and their respective derivatives.