In this paper, we present a critical review on the applications of the Laser-Induced Breakdown Spectroscopy (LIBS) technique in cultural heritage and archaeology. The strategies used by the groups involved in this kind of research for the analysis of the typical materials of interest (metals, pigments, pottery, glass, etc.) are discussed in detail, as well as the use of LIBS in combination with other techniques (LIBS and Raman, LIBS and XRF, and LIBS and MS). Specific applications of LIBS as a support for cultural heritage restoration and the application of the technique for the analysis of underwater objects are presented in separate sessions. In conclusion, new trends of LIBS for cultural heritage and archaeology (micro-LIBS analysis, 3D elemental imaging, and surface- and nanoparticle-enhanced LIBS) are introduced and discussed.

This article reports the mapping of the stones, including marbles and brick masonry, used for building the facade of the medieval Church of St. Nicholas (XI century ad), one of the most interesting churches in Pisa, due also to the nearby famous octagonal bell tower. Mapping of stone materials was performed using a computer-aided design (CAD)/geographical information system (GIS) software package for storing and processing spatial information of the ashlars, obtained using three-dimensional (3D) laser-scanning data, combined with high-resolution images, and stone-to-stone observations. Based on collected data, the facade of the Church of St. Nicholas appeared mostly composed of rocks belonging to the metamorphic Tuscan sequence, quartzites, and marbles from Mt. Pisano area. Other types of rocks were also observed, as black limestones quarried at some kilometers northwest from Pisa in the Monti d’Oltre Serchio area, white Apuan marbles and Macigno sandstones. Conversely, intarsia appeared mainly made up of serpentinite and, subordinately, red limestones laid in white Apuan and Mt. Pisano marbles.