Preservation assessment of Miocene-Pliocene tooth enamel from Tugen Hills (Kenyan Rift Valley) through FTIR, chemical and stable-isotope analyses

We investigated fossil tooth enamel of mammals and crocodiles from two Mio-Pliocene East-African formations (Lukeino and Mabaget Fms) using infrared spectroscopy and chemical and stable-isotope analyses. Infrared spectra indicate that the fossil enamel contains biological apatite (bioapatite), without significant secondary carbonate contaminations. Several empirical infrared indexes were used to analyze the crystal-chemical characteristics of enamel. Fossil enamel has less organic matter, water and structural carbonate of apatite than modern enamel with which it was compared. Fossil apatite has a better crystallinity than bioapatite. The calcium/phosphorus mass ratio and the fluorine content of fossil apatite show intermediate values between bioapatite and geological fluorapatite. The samples also display significant crystal-chemical variations, depending on the vertebrate group (mammals vs. reptiles) and the taphonomic context (Lukeino Fm vs. Mabaget Fm). In spite of these changes, no relationship was observed between the chemical contents (carbonate and fluorine) and the stable-isotope ratios of carbonate (δ¹³C and δ¹⁸O) in fossil enamel. Preservation of the palaeoenvironmental signals is strongly supported by the fact that the stable-isotope composition of the three investigated fossil mammalian taxa (deinotheres, equids and hippos) is consistent with their ecological features. For instance, typical C₃- and C₄-plant isotope compositions are reflected in the deinotheres and equids, respectively, and amphibious hippos display lower δ¹⁸O values than terrestrial herbivores, as expected.