A follow-up on the analytical study of discolouration of the marble statues of Orsanmichele in Florence.

The research complements the complex study carried out to understand the source of brown discolourations of ten marble statues in the Church of Orsanmichele in Florence, Italy. Originally located in exterior niches, the statues were restored to reverse the extensive alterations they had undergone throughout the centuries. One of the major alterations was the application of a dark brown patina that dated just after 1789. After the statues were placed indoors, brownish discolourations started to appear on their surfaces. Cross sections were examined using FTIR mapping and immunological methods. In parallel, the pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) data already obtained from the statues' scrapings were compared with data from aged casein films applied to microscope glass slides and aged milk-treated marble. All the statues had been treated with milk-based substances before the time the bronze patina was applied. The values of temperature and illumination of the room were important factors in the ageing of organic substances and in the formation of calcium oxalates. It is likely that products of thermo-oxidation and photo-oxidation of the oils together with the oxalates caused the darkening. The marble samples corresponded to a Lunense provenance.