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.

Geostatistical spatiotemporal analysis of air temperature as an aid to delineating thermal stability zones in a potential show cave: implications for environmental management.

Air temperature in several galleries of the Covadura System (Sorbas Gypsum Karst, Almería) was measured at monthly intervals over a period of 1 year. The spatial temperature distribution for each month was modeled in a geostatistical framework. The mean trend of the air temperature and the difference between each experimental temperature measurement and this trend were calculated over space and time. Both the trend and residual component were characterized using a geostatistical space-time model. A large spatial trend of the air temperature was found due to the orientation of galleries within the cave system and as a function of the distance from the main cave entrance. Kriging was used for the spatial estimation of the time covariance of the residuals. This enabled the delimitation of the cave into three zones of varying environmental risk in the event of being opened to visits by the public, according to the degree of stability of air temperature over space and time. The influence of human presence on the spatial temperature distribution was assessed using data collected during a year (2000/2001) in pilot galleries opened to the public. An average visit corresponding to August was selected comprising 16 people over a period of 53 min. This average visit influenced the spatial temperature pattern at distances of more than 90 m from the cave entrance, according to the geostatistical model adopted. Within this zone the mean thermal increment generated by human presence was estimated to be 0.26 degrees C. The spatiotemporal mathematical model of the cave air temperature has been revealed as a useful tool for the environmental management of show caves.