Micro-chemical investigation of corrosion products naturally grown on archaeological Cu-based artefacts retrieved from the Mediterranean sea

The corrosion products naturally formed on archaeological Cu-based artefacts during their long-term exposure to seawater have been investigated in details by means of X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersive spectrometry (SEM + EDS), optical microscopy (OM), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential thermal analysis-thermogravimetry (DTA-TG), inductively coupled plasma mass spectrometry (ICP-MS) and X-ray photoelectron spectroscopy (XPS). The bronze artefacts include fragments of valuable statues and objects that were retrieved some decades ago from different seabeds along the Italian coast of the Mediterranean basin including the so called "Punta del Serrone" area (Apulia), the Sicilian channel (Sicily) and the Arburese coast (Sardinia). Our findings show that the alloy matrix is often heavily corroded also in the bulk and reveal the dangerous presence of chlorine from seawater as main dangerous corrosive agent. Chlorine is present as copper nantokite (CuCl) in the inner layers of the patina and is potentially inducing with oxygen and moisture the cyclic and often relentless copper degradation phenomenon commonly called "bronze disease". The most common corrosion products are also lead carbonate (cerussite, PbCO3) and aragonite (CaCO3), likely related to the large abundance of CO2 in the seawater where is assimilated much more than in fresh water. Furthermore, the results reveal that other environmental elements contributing to the composition of the patina are sulphur, magnesium and phosphorous thus giving rise to a patina with a chemically and structurally complex structure. The results reveal also the contribution of bio-organism to the formation of the patina as supported by the presence of vanadium and copper sulphides. These information allow, as a whole, to propose a tentative correlation between the patina's nature, the chemical composition and metallurgical features of the alloys and the marine environment where the objects lived for about two thousands years. From a conservation point of view, the findings reported in this work can provide some insights useful to tailor more efficient conservation strategies with the purpose to ensure a long-term chemical-physical stability to the bronze artefacts.