Quantitative laser induced breakdown spectroscopy analysis of ancient marbles and corrections for the variability of plasma parameters and of ablation rate{

White marble samples from ancient quarries have been analyzed by Laser Induced Breakdown Spectroscopy (LIBS) both on the bulk material and surface encrustations. With the aim to achieve quantitative results by LIBS, until now not reported on marble materials, calibration standards with CaCO3 matrices doped with certified soils were realized. Very different emission intensities and plasma parameters were observed on the standards and natural marbles. In order to compare so different spectra, a method for data analysis was developed, which takes into account variability of the ablation rate, plasma temperature and electron density. It was experimentally demonstrated that ablated volume is well correlated to the emission intensity of plasma continuum for a wide range of laser energies. LIBS signal normalization on the adjacent continuum level, together with introduction of correction factors dependent on plasma parameters, allowed the measuring of concentrations both for major and trace elements in marbles. The analytical procedure was validated by comparative SEM-EDX and ICP-OES measurements. Quantitative LIBS analyses were also performed during encrustation removal and could be applied to control laser-cleaning processes. The quantification of metal contents in the encrustations supported the occurrence of sulfates in the outer layers exposed to environmental agents via a catalytic process.