Laser induced micro-photoluminescence of marble and application to authenticity testing of ancient objects

For the last 70 years, the authenticity of disputable marble objects has been tested by using a black light lamp. According to empirical observations “fresh marbles are purple while ancient ones are blue under the lamp”. This discrimination lacks scientific basis but is very popular because sculptured stone dating is impossible. This work aims to test the reliability of the “UV method” by studying the laser excited photoluminescence (PL) of marble surfaces. An argon ion laser beam was focused through a microscope objective onto the sample, offering a PL spatial resolution of 3 μm. Newly-cut marbles show an intense emission at 610 nm ascribed to Mn²⁺ and a less intense one at 390 nm. Excavated surfaces show the 610 nm emission and a broadband (380–530 nm) one. Similar broadband emissions due to humic (HAs) and fulvic acids (FAs) are typical in soil PL spectra and were observed in the spectra of samples taken from the soil surrounding the excavated surfaces. Additionally, electron paramagnetic resonance (EPR) spectra of excavated surfaces show a peak at g=2.0045, typical in calcite doped with humic acids. We presume that the 380–550 nm emission originates from HA and FA salts existing in the infiltrated soil or the recrystallised calcite developed in marble patinas. Finally, the application of the “UV method” on twelve ancient and modern surfaces proved that the technique is only partly reliable and should be used together with other analytical techniques. PACS 78.55.-m; 78.55.Hx; 81.70.Fy; 87.64.Hd