Laser cleaning of historical limestone buildings in Bordeaux appraisal using cathodoluminescence and electron paramagnetic resonance.

BACKGROUND: Most historical buildings in Bordeaux city are made of limestone. This yellowish-white rock is rather porous and highly sensitive to pollution. As a consequence of local weathering conditions, these buildings present a dark appearance due to the development of a superficial dark grey to black crust.
METHODS: For the last decade, a campaign has been underway to clean these buildings. Eleven techniques of surface treatment have been used, including laser beam technology. As a contribution to the study of laser beam effects on stone buildings, two analytical methods have been used on clean versus unclean surfaces: Cathodoluminescence (CL) and Electron Paramagnetic Resonance (EPR), in addition to SEM-EDX and XRD.
RESULTS: The black crust is composed of different types of particles: carbon porous micro-particles of industrial origin, atmospheric dust due to the erosion of soils and rocks, alumino-silicate particles from urban pollution; all these particles being cemented by gypsum. DISCUSSION: As far as heritage conservation is concerned, the laser surface treatment not only preserves the original patina of the stone, but also leaves surface smoothness unaltered. CONCLUSIONS AND PERSPECTIVES: CL and EPR data confirm that lasers--with highly controlled parameters--only get rid of the black crust and, thus, reveal the underneath layer, the so-called patina. This patina shows no luminescence, whereas the limestone on which it has grown shows a bright orange emission of CL. This indicates CL to be a fast and easy way to provide a high quality control for the restoration of polluted ancient stones.