Johannes Vermeer (1632–1675) is known for his brilliant blue colours, and his frequent use of the costly natural ultramarine. This paper reveals new findings about ultramarine in the headscarf of Girl with a Pearl Earring (c. 1665, Mauritshuis). The painting was examined using a range of micro- and macroscale techniques as part of the Girl in the Spotlight research project (2018). Analysis of micro-samples mounted as cross-sections using SEM–EDX and FTIR-ATR showed that Vermeer used high-quality ultramarine in the blue headscarf, based on the relative abundance of bright blue particles of lazurite. Analysis with synchrotron sulphur K-edge XANES suggested that the ultramarine pigment was prepared—at least in part—from a heat-treated lapis lazuli rock. The entire painting was imaged using MS-IRR, MA-XRF, RIS, and digital microscopy to reveal the distribution of materials of the headscarf, and to give more insight into Vermeer’s painting process. The shadow part of the headscarf has a remarkably patchy appearance, due to paint degradation that is probably related to the large amounts of chalk Vermeer mixed in the ultramarine paint in this area. The question was raised as to whether extra chalk was added deliberately to the paint to adjust the handling properties or opacity, or whether the chalk was the substrate of a—now faded—yellow lake. Schematic paint reconstructions were made to investigate the effect of the addition of chalk or yellow lake on the paint properties. The analyses and reconstructions led to the hypothesis that the blue headscarf originally contained a wider range of different blue colour shades: an opaque light blue for the left (lit) zone, a slightly brighter opaque blue for the middle zone, and a deep dark blue-green glaze with alternating blue-green glazing brushstrokes for the shadow zone—now largely compromised by paint degradation.

The background of Vermeer’s Girl with a Pearl Earring (c. 1665, Mauritshuis) has, until recently, been interpreted as a flat dark space. The painting was examined in 2018 as part of the research project The Girl in the Spotlight using a combination of micro- and macro-scale analytical techniques. The stratigraphy of the background was determined from samples mounted as cross-sections, and its material composition was analysed using electron microscopy and chromatographic techniques. The underlayer contains mainly charcoal black, and the glaze contains two organic colourants—indigo and weld—and a copper drier. Deterioration of the glaze has made features in the background difficult to discern with the naked eye. Complementary imaging techniques were able to visualise Vermeer’s signature, and the suggestion of folded fabric (possibly a curtain) on the right side of the painting. The distribution of the layer(s) in the background were imaged using: infrared reflectography (900–1100 nm), multi-scale optical coherence tomography scanning, macroscopic X-ray fluorescence and 3D digital microscopy. Vermeer applied the black underlayer vigorously with overlapping brushstrokes that varied in thickness. When he applied the glaze on top, it levelled out to make a smooth flat surface. The visual effect of the background contrasts the figure of the Girl and projects her forward in space, closer to the viewer.