Characterizing Modern and Fossil Gymnosperm Exudates Using Micro-Fourier Transform Infrared Spectroscopy

Abstract

Infrared absorption spectra of exudates from 65 species of gymnosperms were measured using micro–Fourier transform infrared (FTIR) spectroscopy. On the basis of the infrared spectra, three compositionally distinct groups of exudates can be distinguished: resins, volatile-rich resins, and gums. Resins and volatile-rich resins are mainly composed of terpenoids, whereas gums are polysaccharides. Resins and volatile-rich resins are restricted to conifers (Pinophyta). Gums, on the other hand, are produced by some conifer families including Araucariaceae and Podocarpaceae; nonconifer gymnosperms including Ginkgo (Ginkgophyta), cycads (Cycadophyta), and Welwitschia (Gnetophyta); and angiosperms. Using spectral band ratios, conifer resins can be subdivided quantitatively into two distinct resin types that reflect compositional differences in their terpenoid constituents and broadly parallel different conifer families. The first type of resin (pinaceous resin) is produced by members of Pinaceae and consists mainly of diterpenes that are based on abietane/pimarane skeletal structures. The second type (cupressaceous resin) is associated with members of the Cupressaceae, Sciadopityaceae, Araucariaceae, and Podocarpaceae and consists mainly of diterpenes that are based on the labdanoid structures. Variability within the resin spectra correlates with the number of free hydroxyl groups, and it can be used to assess the degree of resin polymerization. Volatile-rich resins are found exclusively within Pinaceae, reflecting a generally higher abundance of volatile mono- and sesquiterpenoids in resins of this family. The results of the FTIR spectroscopy have direct implications for the assessment of the fossil potential and the chemotaxonomic interpretation of modern and fossil gymnosperm exudates.