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.

A short review on LIBS industrial applications.

The usual approach to laser-induced breakdown spectroscopy (LIBS) quantitative analysis is based on the use of calibration curves, suitably built using appropriate reference standards. More recently, statistical methods relying on the principles of artificial neural networks (ANN) are increasingly used. However, ANN analysis is often used as a 'black box' system and the peculiarities of the LIBS spectra are not exploited fully. An a priori exploration of the raw data contained in the LIBS spectra, carried out by a neural network to learn what are the significant areas of the spectrum to be used for a subsequent neural network delegated to the calibration, is able to throw light upon important information initially unknown, although already contained within the spectrum. This communication will demonstrate that an approach based on neural networks specially taylored for dealing with LIBS spectra would provide a viable, fast and robust method for LIBS quantitative analysis. This would allow the use of a relatively limited number of reference samples for the training of the network, with respect to the current approaches, and provide a fully automatizable approach for the analysis of a large number of samples

In this work, a critical review of the current nondestructive probing and image analysis approaches is presented, to revealing otherwise invisible or hardly discernible details in manuscripts and paintings relevant to cultural heritage and archaeology. Multispectral imaging, X-ray fluorescence, Laser-Induced Breakdown Spectroscopy, Raman spectroscopy and Thermography are considered, as techniques for acquiring images and spectral image sets; statistical methods for the analysis of these images are then discussed, including blind separation and false colour techniques. Several case studies are presented, with particular attention dedicated to the approaches that appear most promising for future applications. Some of the techniques described herein are likely to replace, in the near future, classical digital photography in the study of ancient manuscripts and paintings.