On the influence of relative humidity on the oxidation and hydrolysis of fresh and aged oil paints

Modern oil paintings are affected by conservation issues related to the oil paint formulations and to the fact that they are often unvarnished, and in direct contact with the environment. Understanding the evolution of the molecular composition of modern oil paint during ageing, under the influence of environmental factors, is fundamental for a better knowledge of degradation phenomena and risk factors affecting modern art. We investigated for the first time the influence of relative humidity on the chemical composition of modern oil paints during curing and artificial ageing. For this purpose, modern oil paint layers naturally aged for 10 years were further artificially aged in low and high relative humidity conditions. Moreover, the influence of RH% on the curing of fresh paint layers was studied. The paints used in the experiments are from three suppliers (Old Holland, Winsor≠wton, and Talens), and contain cadmium or cadmium zinc sulfide as main pigment. The changes in the composition of extracts of paint samples were investigated by direct electrospray mass spectrometry with a quadrupole-time of flight mass analyser (ESI-Q-ToF). The obtained mass spectral data were interpreted by means of principal component analysis (PCA) operated on a data set containing the relative abundance of ions associated to significant molecules present in the extracts, and also by calculating the ratios between the signals relative to fatty acids, dicarboxylic acids and acylglycerols, related to hydrolysis and oxidation phenomena. The same paint samples were also analysed, in bulk, by pyrolysis gas chromatography mass spectrometry (Py-GC/MS), achieving chemical information on the total lipid fraction. High performance liquid chromatography (HPLC) ESI-Q-ToF was carried out for the characterisation of the profile of free fatty acids (FFA) and acylglycerols, defining the nature of the oils used in the paint formulations, and for the determination of the degree of hydrolysis. This study demonstrated that relative humidity conditions significantly influence the chemical composition of the paints. Ageing under high RH% conditions produced an increase of the formation of dicarboxylic acids compared to ageing under low RH%, for all paints, in addition to a higher degree of hydrolysis, followed by evaporation of free fatty acids.