Wetest 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 nitrateminerals
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, SWSpain). Unusual cavemineralswere 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.
