The archaeological site known as Toca do Enoque (geographical coordinates, 09 • 14 65.3 S 43 • 55 62.5 W) is a rock shelter located in the Serra das Andorinhas (Serra das Confusões National Park), rural area of the city of Guaribas, state of Piauí, Brazil. Several rupestrian paintings (anthropomorphic and zoomorphic motifs along with some pure graphisms), predominantly in red, are found on the sandstone walls. Charcoals, lithic materials, necklaces with teeth, animal bones, gastropod shells, ochres and human skeletons (dated from 6,220 ± 40 to 6,610 ± 40 years before present, BP) were identified in recent excavations in this shelter. Red and yellow ochre samples were collected from prehistoric funeral structures and L. C. Duarte Cavalcante et al. Fig. 1 Map of the Parque Nacional Serra das Confusões and Toca do Enoque site analyzed with powder X-ray diffractometry, Fourier-transform infrared spectroscopy and 57 Fe transmission Mössbauer spectroscopy at 298 K and 80 K. Mössbauer data indicate that the red ochre do contain predominantly hematite (α-Fe 2 O 3 ) whereas goethite (α-FeOOH) is the major mineral in the yellow ochre.