Spectroscopic Monitoring of the Laser Cleaning Applied to Ancient Marbles from Mediterranean Areas

Abstract

Laser Induced Breakdown Spectroscopy (LIBS) analysis by Nd:YAG laser emitting at 355nm were performed on different clean and dirty surfaces of marble fragments collected from ancient quarries in Greece, Turkey and Italy, in order to determine semi-quantitavely the atomic composition of the bulk material and encrustation. The method here developed for element concentrations retrieval could be applied during laser cleaning process to supply the information about the effective crust composition at different depths and the point where the process should be interrupted. The knowledge of the crust composition along successive layers is also important for determining the restoration procedures. The elements measured in the encrustations, such as Si, Al, Ca, C, Ti, Mn, Mg, Na, Ba, Sr and Cu are also present in the bulk, but at different concentrations whose determination allows for the process monitoring. The only element here observed in the crusts and not detected in the bulk materials is Chromium, whose progressive disappearance from LIBS spectra could be used as another indicator of the laser cleaning effectiveness. On a sample from Turkey also Vanadium was detected in the encrustation. The present LIBS measuring method was validated by SEM-EDX and ICP analyses. The clean marble surface and encrustations were further analysed by Laser Induced Fluorescence (LIF), which could be used as an alternative technique for the on-line control of the cleaning effectiveness. Better discrimination between dirty and clean marble surface was obtained when 266nm excitation was applied instead of 355 nm. Characteristic LIF spectral signatures allows for the discrimination between different type of the natural stones, even under the water.