In this study, Raman microspectroscopy is applied to investigate two manganese oxide phases: lithiophorite [(Al,Li)Mn 4+ O 2 (OH) 2 ] and asbolane [(Ni,Co) x Mn 4+ (O,OH) 4 ·nH 2 O], along with their intermediates ('asbolane-lithiophorite intermediates': ALI). These oxides typically incorporate variable concentrations of Co, Ni, Cu and Li. They represent a group of economically interesting phases that are difficult to identify and characterize with classical X-ray diffraction techniques. We show that Raman micro spectroscopy is useful to the investigation of those phases, but they require to be tested in very low laser power conditions to avoid sample degradation (e.g. 0.2 mW with λ = 532 nm). We propose reference Raman spectroscopic signatures for lithiophorite, asbolane and ALI phases. These spectra are mainly composed of two spectral domains, the first one is located between 370 and 630 cm À1 and the second one between 900 and 1300 cm À1 . We then assess the impact of their highly variable chemistry on their Raman peak positions, intensities and FWHM using a semi-systematic curve-fitting method profiled for these phases.

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Despite uncontested evidence for fossils belonging to the early hominin genus Australopithecus in East Africa from at least 4.2 million years ago (Ma), and from Chad by 3.5 Ma, thus far there has been no convincing evidence of Australopithecus, Paranthropus or early Homo from the western (Albertine) branch of the Rift Valley. Here we report the discovery of an isolated upper molar (#Ish25) from the Western Rift Valley site of Ishango in Central Africa in a derived context, overlying beds dated to between ca. 2.6 to 2.0 Ma. We used µCT imaging to compare its external and internal macro-morphology to upper molars of australopiths, and fossil and recent Homo. We show that the size and shape of the enamel-dentine junction (EDJ) surface discriminate between Plio-Pleistocene and post-Lower Pleistocene hominins, and that the Ishango molar clusters with australopiths and early Homo from East and southern Africa. A reassessment of the archaeological context of the specimen is consistent with the morphological evidence and suggest that early hominins were occupying this region by at least 2 Ma.