High-resolution fluorescence mapping of impurities in historical zinc oxide pigments: hard X-ray nanoprobe applications to the paints of Pablo Picasso

Here for the first time we describe the use of high resolution nanoprobe X-ray fluorescence (XRF) mapping for the analysis of artists’ paints, hierarchically complex materials typically composed of binder, pigments, fillers, and other additives. The work undertaken at the nanoprobe sought to obtain highly spatially resolved, highly sensitive mapping of metal impurities (Pb, Cd, Fe, and other metals) in submicron particles of zinc oxide pigments used in early 20th century artists’ tube paints and enamel paints, with particular emphasis on Ripolin, a popular brand of French house paint used extensively by Pablo Picasso and some of his contemporaries. Analysis revealed that the Zn oxide particles only contain a little Fe, proving that the highest quality Zn oxide pigment, free of Pb and Cd, was used for Ripolin house paints as well as artists’ paints. Nanoprobe XRF mapping also demonstrated that artists’ tube paints generally have more abundant fillers and additional whites (based on Pb, Ti, Ca) than Ripolin paints, which contain mostly pure zinc oxide. The chemical characterization of paints at the nanoscale opens the path to a better understanding of their fabrication and chemical reactivity.