Comparative laser spectroscopy diagnostics for ancient metallic artefacts exposed to environmental pollution

Metal artworks are subjected to corrosion and oxidation processes due to reactive agents present in the air, water and in the ground that these objects have been in contact with for hundreds of years. This is the case for archaeological metals that are recovered from excavation sites, as well as artefacts exposed to polluted air. Stabilization of the conservation state of these objects needs precise diagnostics of the accrued surface layers and identification of original, historical materials before further protective treatments, including safe laser cleaning of unwanted layers. This paper presents analyses of the chemical composition and stratigraphy of corrosion products with the use of laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy. The discussion of the results is supported by material studies (SEM-EDS, XRF, ion-analyses). The tests were performed on several samples taken from original objects, including copper roofing from Wilanów Palace in Warsaw and Karol Poznański Palace in ŁódŸ, bronze decorative figures from the Wilanów Palace gardens, and four archaeological examples of old jewellery (different copper alloys). Work has been performed as a part of the MATLAS project in the frames of EEA and Norway Grants (www.matlas.eu) and the results enable the comparison of the methodology and to elaborate the joint diagnostic procedures of the three project partner independent laboratories.