Electron energy loss spectroscopy elucidates the elusive darkening of zinc potassium chromate in Georges Seurat's A Sunday on La Grande Jatte--1884.

The color darkening of selected brushstrokes of Georges Seurat's A Sunday on La Grande Jatte--1884 was noted as early as 1892. Artificial aging of model systems containing zinc yellow (K(2)O·4ZnCrO(4)·3H(2)O) mixed with linseed oil successfully replicated the phenomena observed on La Grande Jatte. Electron energy loss spectroscopy measurements performed on the uppermost few microns of thin sections of the paint layers (obtained with focused ion beam milling) determined that samples which turned olive green (aged at 90% RH, with SO(2) and light) contain mostly the altered species Cr(III) and that the ochre-yellow coloration of specimens aged at 50% RH with SO(2) and light is due to the presence of dichromate ions (Cr (VI)). The altered species are only present in the first few microns of paint and are likely poorly crystalline, so that they eluded other types of bulk and surface measurements, but they create a substantial color alteration at the surface of the paint films. A similar phenomenon was confirmed on a sample from La Grande Jatte, where Cr(III) and Cr(VI) dichromate ions were detected in the ochre-colored, altered brushstrokes of zinc yellow. Laboratory simulations demonstrated that the equilibrium between chromate and dichromate ions is reversible within the paint film and that the orange dichromate ions can be transformed back into bright yellow chromates by exposure to highly alkaline gases.