Protein diagenesis in Patella shells: implications for amino acid racemisation dating

Se analiza la racemización de aminoácidos en proteínas inter e intracristalinas en conchas de Patella y su utilización como herramienta geocronológica, fundamentalmente empleadas en yacimientos arqueológicos.The inter- and intra-crystalline fractions of Patella vulgata limpets recovered from archaeological sites in Northern Spain (covering Neolithic, Mesolithic, Magdalenian, Solutrean, and Aurignacian periods) were examined for amino acid composition and racemisation over time. The calcitic apex and rim areas of the shells were found to probably be composed of similar proteins, as the D/L values and amino acids were comparable and varied in the same way with increasing age; however, the mineral structures present in these areas differed. The aragonitic intermediate part of the shell showed a distinctly different amino acid composition and mineral structure. The main protein leaching from the inter-crystalline fraction occurred within the first 6000 yr after the death of the organism. In contrast, the intra-crystalline fraction — comprised of a different protein composition than the inter-crystalline fraction — appeared to behave as a closed system for at least 34 ka, as reflected by the lack of a significant decrease in the amino acid content; however, changes in the amino acid percentages occurred during this period. The concentration of aspartic acid remained almost constant with age both in inter- and intra-crystalline proteins, and its contribution to the total amino acid content increased with age at the expense of other amino acids such as glutamic acid, serine, glycine and alanine. Temperature is thought to play a key role in the amino acid racemisation of P. vulgata and could explain why in the localities belonging to the Gravettian and Solutrean period, which formed during relatively cold conditions, D/L values were similar to those detected in shells from sites formed during the Magdalenian.

Lithic economy and territory of Epipaleolithic hunter–gatherers in the Middle Tagus: The case of Pena d'Água (Portugal)

In Central Portugal (westernmost Eurasia) the transition from the traditional Pleistocene hunter–gatherer societies to the complex Mesolithic societies of the Holocene has been debated for decades. While some argue that these differences were a progressive phenomenon that started with the shift from the Pleistocene to the Holocene, others defend that the Late Pleistocene patterns were fairly similar to those of the Epipaleolithic and that the major shift was rapid, dramatic and triggered by the necessary adaptation to the 8.2 ka cal BP (8.09–8.25 ka cal BP) climatic event. The study of lithic raw material provenance might be useful for this discussion, since it has been suggested that the Magdalenian and Epipaleolithic populations from this region were collecting this resources within a close range territory, whereas the Mesolithic populations were acquiring them at longer distances. In this paper, we present the results from p-XRF, VP-SEM-EDS and μ-XRD analysis done on the Epipaleolithic lithic assemblage from Pena d'Água Rockshelter, and in some geological samples from secondary sources located ∼14 km from this site. This layer is of major relevance for this debate since it is dated from 8.19 ka cal BP. If the transition was gradual, it would be expected that this assemblage would show some traits of higher-complexity seen in the Mesolithic, namely of longer distance acquisition. However, our results indicate correspondence between the archaeological chert types and some of the geological sources. The differences seen between the archaeological specimens and geological samples are mostly present in traits that can be related with manufacture, handling and post-depositional phenomena. The results suggest that, in what concerns to the economy of abiotic resources, the Epipaleolithic populations living at the time of the dramatic 8.2 ka cal BP cold event, were performing a short range acquisition of lithic raw materials which reinforces the idea of continuity from the Late Pleistocene to the 8.2 ka cal BP event and an abrupt and dramatic shift soon after this phenomena.