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Lead white, a mixture of cerussite (PbCO3) and hydrocerussite (2PbCO3·Pb(OH)2), is the most ancient and common white pigment used in mural paintings. However, it tends to blacken with time due to its oxidation to plattnerite (β-PbO2). Chemical treatments were used but they can put the pictorial layers supports at risks. Hereby, we address the possibility of thermally reconverting black plattnerite to white lead carbonates via a massicot (β-PbO) intermediate. We first investigated the conditions (temperature, time, and environment) in which pure powders react, before studying mural painting samples. Experiments were made in ovens and thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) characterisation were achieved. Litharge (α-PbO) and massicot were obtained from plattnerite, respectively, between 564 and 567 °C and at 650 °C. Lead carbonates, namely cerussite, hydrocerussite and plumbonacrite (3PbCO3·Pb(OH)2·PbO) formed from massicot in wet CO2 below 100 °C in a few hours. Lastly, when heating plattnerite-based mural painting samples, lead species reacted with binders and mortar, yielding massicot, plumbonacrite but also lead silicate and calcium lead oxides. This demonstrates the viability of thermal reconversion of darkened lead in mural, while raising concerns about the formation of several lead species by reaction with mural painting constituents. [ABSTRACT FROM AUTHOR]

Red lead and lead white are some of the most ancient and common pigments in mural paintings. However, they tend to blacken with time due to their oxidation to plattnerite (β-PbO2). The possibility to induce the reconversion reactions by CW laser heating is hereby discussed. A thermodynamic study by TGA showed that direct cerussite or hydrocerussite formation from plattnerite are not suitable reconversion routes, which was confirmed by laser irradiation trials under CO2 and CO2/H2O fluxes. Minium (Pb3O4) and subsequent massicot (β-PbO) formation from plattnerite were achieved (confirmed by SEM–EDS, XRD and micro-Raman) under Ar+, 810 nm diode and Nd:YAG lasers. The latter appears to be the most suited for restauration purposes, given the broad minium reconversion irradiance range. This is confirmed by successful trials on macroscopic areas of naturally darkened red lead containing samples. [ABSTRACT FROM AUTHOR]