In situ Raman characterization of minerals and degradation processes in a variety of cultural and geological heritage sites.

We test the capabilities of in situ Raman spectroscopy for non-destructive analysis of degradation processes in invaluable masterpieces, as well as for the characterization of minerals and prehistoric rock-art in caves. To this end, we have studied the mechanism of decay suffered by the 15th-century limestone sculptures that decorate the retro-choir of Burgos Cathedral (N Spain). In situ Raman probe detected hydrated sulfate and nitrate minerals on the sculptures, which are responsible for the decay of the original limestone. In addition, in situ Raman analyses were performed on unique speleothems in El Soplao Cave (Cantabria, N Spain) and in the Gruta de las Maravillas (Aracena, SW Spain). Unusual cave minerals were detected in El Soplao Cave, such as hydromagnesite (Mg5(CO3)4(OH)2·4H2O), as well as ferromanganese oxides in the black biogenic speleothems recently discovered in this cavern. In the Gruta de las Maravillas, gypsum (CaSO4·2H2O) was identified for the first time, as part of the oldest cave materials, so providing additional evidence of hypogenic mechanisms that occurred in this cave during earlier stages of its formation. Finally, we present preliminary analyses of several cave paintings in the renowned "Polychrome Hall" of Altamira Cave (Cantabria, N. Spain). Hematite (Fe2O3) is the most abundant mineral phase, which provides the characteristic ochre-reddish color to the Altamira bison and deer paintings. Thus, portable Raman spectroscopy is demonstrated to be an analytical technique compatible with preserving our cultural and natural heritage, since the analysis does not require physical contact between the Raman head and the analyzed items.

U-series dating of Paleolithic art in 11 caves in Spain.

Paleolithic cave art is an exceptional archive of early human symbolic behavior, but because obtaining reliable dates has been difficult, its chronology is still poorly understood after more than a century of study. We present uranium-series disequilibrium dates of calcite deposits overlying or underlying art found in 11 caves, including the United Nations Educational, Scientific, and Cultural Organization (UNESCO) World Heritage sites of Altamira, El Castillo, and Tito Bustillo, Spain. The results demonstrate that the tradition of decorating caves extends back at least to the Early Aurignacian period, with minimum ages of 40.8 thousand years for a red disk, 37.3 thousand years for a hand stencil, and 35.6 thousand years for a claviform-like symbol. These minimum ages reveal either that cave art was a part of the cultural repertoire of the first anatomically modern humans in Europe or that perhaps Neandertals also engaged in painting caves.