Investigation of the Discoloration of Smalt Pigment in Historic Paintings by Micro-X-ray Absorption Spectroscopy at the Co K-Edge

Smalt was commonly used as a pigment by artists between the 16th and 18th centuries. It is a powdered blue potash glass colored by cobalt ions and often degrades causing dramatic changes in the appearance of paintings. The aim of the work presented in this paper was to investigate the changes in the structure and environment around the cobalt ion on deterioration, to further our understanding of the basis of the loss of color. Particles of well-preserved and altered smalt in microsamples from paintings in the National Gallery, London, and the Louvre, Paris, were analyzed using synchrotron micro-X-ray absorption spectroscopy at the Co K-edge. X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) measurements showed that in intense blue particles the cobalt is predominantly present as Co2+ in tetrahedral coordination, whereas in colorless altered smalt the Co2+ coordination number in the glass structure is increased and there is a shift from tetrahedral toward octahedral coordination. The extent of this shift correlates clearly with the alkali content, indicating that it is caused by leaching of potassium cations, which act as charge compensators and stabilize the tetrahedral coordination of the cobalt ions that is responsible for the blue color.