As part of the NWO Science4Arts REVISRembrandt project (2012–2018), novel chemical imaging techniques were developed and applied to the study of Rembrandt’s late experimental painting technique (1651–1669). One of the unique features in his late paintings is his abundant use of smalt: a blue cobalt glass pigment that he often combined with organic lake pigments, earth pigments and blacks. Since most of these smalt-containing paints have discolored over time, we wanted to find out more about how these paintings may have originally looked, and what the role of smalt was in his paint. This paper reports on the use of smalt in complex pigment mixtures in Rembrandt’s Homer (1663), Mauritshuis, The Hague. Macroscopic X-ray fluorescence imaging (MA-XRF) assisted by computational analysis, in combination with SEM-EDX analysis of paint cross-sections, provides new information about the distribution and composition of the smalt paints in the painting. Paint reconstructions were carried out to investigate the effect of different percentages of smalt on the overall color, the drying properties, translucency and texture of the paint. Results show that the influence of (the originally blue) smalt on the intended color of the paint of the Homer is minimal. However, in mixtures with high percentages of smalt, or when combined with more transparent pigments, it was concluded that the smalt did produce a cooler and darker paint. It was also found that the admixture of opaque pigments reduced the translucent character of the smalt. The drying tests show that the paints with (cobalt-containing) smalt dried five times faster compared to those with glass (without cobalt). Most significantly, the texture of the paint was strongly influenced by adding smalt, creating a more irregular surface topography with clearly pronounced brushstrokes. Optical coherence tomography (OCT) was used as an additional tool to reveal differences in translucency and texture between the different paint reconstructions. In conclusion, this study confirmed earlier assumptions that Rembrandt used substantial amounts of smalt in his late paintings, not for its blue color, but to give volume and texture to his paints, to deepen their colors and to make them dry faster.

Direct temperature-resolved mass spectrometry (DTMS) is an analytical technique in which small (μg) amounts of sample are applied to a filament and introduced into the ion source of a mass spectrometer. It is a fast fingerprinting method particularly suitable for the characterization of oils, resins, waxes, and other compound classes in tiny complex samples from paintings. DTMS results reported thus far have been obtained using instruments with nominal mass resolution. Higher mass resolutions can be achieved by magnetic sector mass spectrometers only at the expense of a severe loss of sensitivity. Modern time-of-flight mass spectrometers, however, do provide both high resolution and high sensitivity simultaneously. The availability of accurate mass information adds another dimension to DTMS. The difference between the nominal and accurate mass, the mass defect, may be graphically presented in so-called ‘Kendrick plots’. These can be used as fingerprints, enabling a quick overview of the main features in high-resolution mass spectra of complex mixtures. This paper combines DTMS with Kendrick mass defect analysis applied to a series of reference compounds commonly found in paintings. Finally, we also present the results of analysis of samples taken from the 17th-century painting of Saul and David by Rembrandt van Rijn (Mauritshuis, The Hague) that has been recently subjected to extensive conservation treatment.