Unraveling the role of the thermal and laser impacts on the blackening of cinnabar in the mural paintings of Pompeii

Abstract

The blackening of red cinnabar (α-HgS) pigment has traditionally been explained by its conversion into black metacinnabar (β-HgS). Scarce is however the scientific evidence that supports this hypothesis in polychrome artworks. As such transition occurs at around 345 °C, the thermal impact of the eruption of Mount Vesuvius in 79 AD could have induced this structural change of the pigment present in the mural paintings of Pompeii. This work aims to assess whether the mentioned volcanic eruption could be responsible of the cinnabar blackening through the formation of metacinnabar. The thermodiffractometry study of cinnabar-decorated fresco mock-ups stated that the formed β-HgS is not stable, observing its reversion into α-HgS. Moreover, sublimation of the cinnabar pictorial layer was registered, also when the cinnabar paint layer was protected by a coating of pyroclastic materials. In real blackened cinnabar Pompeian samples, it was not possible to identify metacinnabar by X-ray diffraction (XRD), but evidence of sublimation of mercury due to the thermal impact was observed. Hence, this blackening seems to be related mainly to the presence of calomel (Hg2Cl2) and a gypsum (CaSO4·2H2O) crust as degradation products of red cinnabar and the calcite mortar, respectively, and not to the formation of metacinnabar. Finally, laser-based techniques could also induce modifications in the HgS crystalline structure, resulting in an amorphous black product. Therefore, the elemental and molecular study of the species promoted by laser impact was carried out to avoid false positives in the metacinnabar detection or when the decorated surface has been subjected to laser cleaning.Graphical