Throughout the Neogene, the faunas and floras in Africa recorded global climatic changes. We present an overview of Neogene desertification in Africa by tracing stable isotopes in eggshells and mammalian enamel, by faunal (changes in hypsodonty, etc.) and floral changes in sequences at the latitudinal extremities of the continent and the equator. This work reveals that desertification started in the southwest ca 17-16 Ma, much earlier than the region of the present-day Sahara (ca 8-7 Ma) and long before the deserts in East Africa (Plio-Pleistocene). A consequence of this history is that animals and plants inhabiting the South of the continent had a long period of time in which to adapt to arid, unstable climatic conditions. When parts of East Africa became arid during the Late Miocene and Plio-Pleistocene, several of these lineages expanded northwards and occupied developing arid niches before local lineages could adapt. Several of the latter became extinct, while others withdrew westwards as the tropical forest diminished in extent. It is proposed that the history of desertification in Africa was related to that of the polar ice caps (Antarctic, Arctic).

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International audienceThe crystallinity of natural and synthetic apatite samples is often determined from the broadening of m4 PO4 infrared absorption bands. However, various physical mechanisms contribute to the observed linewidth. In the present study, the factors determining the linewidth in the powder spectrum of synthetic fluorapatite and hydroxyapatite samples are investigated. The temperature dependence of the infrared spectrum (10-270 K) is used to assess the respective contributions of homogeneous broadening, related to the decay of phonons through anharmonic coupling, and heterogeneous broadening related to elastic strain and macroscopic electrostatic effects. This latter contribution is dominant in the investigated samples and depends on the shape of powder particles. It is discussed under the light of the theoretical modeling of the low-frequency dielectric properties of apatite based on first-principles density functional theory calculations. The linewidth of the weak m1 PO4 absorption band provides a reliable information on microscopic sources of broadening, i.e., apatite crystallinity. In comparison, the other more intense PO4 bands are more sensitive to long-range electrostatic effects

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International audienceWe propose a microscopic model of the dominant carbonate for phosphate substitution in fluor- apatite. A well-crystallized sedimentary fluorapatite sample containing ~2.3 ± 0.8 wt% of carbonate was investigated using Fourier transform infrared spectroscopy (FTIR) and ¹³C and ¹⁹F magic angle spinning nuclear magnetic resonance (MAS NMR). About 75% of the carbonate groups replace the phosphate group ("B-site"), whereas a lesser contribution from carbonate groups located in the structural channels ("A-site") is observed. Beside the dominant ¹⁹F NMR signal of channel ions at ~ -102 ppm, an additional signal corresponding to ~8% of fluoride ions is observed at -88 ppm. ¹⁹F double quantum-single quantum (DQ-SQ) MAS NMR and ¹³C{¹⁹F} frequency-selective Rotational Echo DOuble Resonance (REDOR) experiments prove that this additional signal corresponds to iso- lated fluoride ions in the apatite structure, located in close proximity of substituted carbonate groups. Density functional theory (DFT) calculations allow us to propose a composite carbonate-fluoride tetrahedron defect model accounting for these experimental observations. The planar carbonate ion lies in the sloping face of the tetrahedron opposite a fluoride ion occupying the remaining vertex, together replacing the tetrahedral phosphate ion. This "francolite-type" defect leads to a diagnostic narrow IR absorption band at 864 cmĐ¹ that could be used as a guide to, e.g., detect the incipient transformation of fossil bone and teeth samples