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 nonplanar shape of a painting as well as practical constraints often result in the painting's surface not being parallel to the plane in that the measurement head of a MA-XRF scanner is being moved. Changing the working distance affects the measurement geometry, so that the sensitivity for the same element may vary throughout the investigated area and induce visible artifacts. These artifacts are especially visible when different scans of the same painting are stitched together. In this article, we present an approach to correct for the variation of the measurement distance. We explored using an intrinsic part of the XRF data set, the Ar signal from the air, to estimate the distance between surface and instrument. The model is developed based on fundamental parameter calculations and a measurement of a NIST 610 standard and is verified on a set of scans of Rembrandt's ‘Portrait of Oopjen Coppit (1611–1689)’.

Until the 19th century, lead white was the most important white pigment used in oil paintings. Lead white is typically composed of two crystalline lead carbonates: hydrocerussite [2PbCO₃·Pb(OH)₂] and cerussite (PbCO₃). Depending on the ratio between hydrocerussite and cerussite, lead white can be classified into different subtypes, each with different optical properties. Current methods to investigate and differentiate between lead white subtypes involve invasive sampling on a microscopic scale, introducing problems of paint damage and representativeness. In this study, a 17th century painting GirlwithaPearlEarring(by Johannes Vermeer, c. 1665, collection of the Mauritshuis, NL) was analyzed with a recently developed mobile and noninvasive macroscopic x-ray powder diffraction (MA-XRPD) scanner within the project Girl in the Spotlight. Four different subtypes of lead white were identified using XRPD imaging at the macroscopic and microscopic scale, implying that Vermeer was highly discriminatory in his use of lead white.

Traditional “stack “manufacturing process (16–19th c.) of lead white pigment by lead corrosion is explored by exposing metal to acetic acid, carbon dioxide, dioxygen and water vapor. Global reaction scheme is revealed, along with stratification of corrosion products with CO₂ gradient, leading to flakiness of corrosion layer. Kinetic and epitaxial features rule the polyphased structure, explaining hydrocerussite-rich compositions and absence of plumbonacrite in classical easel paintings. Microstructure of cerussite appears as a differentiation criterion between stack-made and industrial precipitation-synthesized lead whites. Particular conditions reported in ancient writings are tested and discussed to understand unusual processes.

Rembrandt (1606–1669) is renowned for his impasto technique, involving his use of lead white paint with outstanding rheological properties. This paint was obtained by combining lead white pigment (a mixture of cerussite PbCO ₃ and hydrocerussite Pb ₃(CO ₃) ₂(OH) ₂) with an organic binding medium, but the exact formulation used by Rembrandt remains a mystery. A powerful combination of high-angle and high-lateral resolution x-ray diffraction was used to investigate several microscopic paint samples from four Rembrandt masterpieces. A rare lead compound, plumbonacrite (Pb ₅(CO ₃) ₃O(OH) ₂), was detected in areas of impasto. This can be considered a fingerprint of Rembrandt's recipe and is evidence of the use of an alkaline binding medium, which sheds a new light on Rembrandt's pictorial technique.

The use of non-invasive macroscopic imaging techniques is becoming more prevalent in the field of cultural heritage, especially to avoid invasive procedures that damage valuable artworks. For this purpose, an X-ray powder diffraction scanner (MA-XRPD) capable of visualising crystalline compounds in a highly specific manner was recently developed. Many inorganic pigments present in paintings fall into this category of materials. In this study, the 17th century oil painting Girl with a Pearl Earring (c. 1665) by Johannes Vermeer was analysed with a combination of transmission and reflection mode MA-XRPD. By employing this scanner in reflection mode, the relative sensitivity for compounds that are present at the paint surface could be increased, establishing it as a highly relevant technique for investigating the degradation processes that are ongoing at paint surfaces. Many of the original pigments employed by Vermeer could be identified, along with four secondary alteration products: gypsum (CaSO₄·2H₂O), anglesite (PbSO₄), palmierite (K₂Pb(SO₄)₂) and weddellite (CaC₂O₄·2H₂O). The formation of gypsum was linked to the presence of chalk in the upper glaze layer while the formation of palmierite and weddellite is driven by the presence of lake pigments (and their substrates). In this manner, MA-XRPD can also be used to pinpoint locations relevant for sampling and synchrotron µ-XRPD analysis, which provides information on the microscopic make-up of the paint. A paint cross-section taken from an area rich in palmierite was analysed with synchrotron µ-XRPD, which confirmed the presence of this secondary compound at the interface of the upper paint layer with the ground layer as well as the presence of anglesite in the ground layer. The capacity of MA-XRPD to identify and chart secondary alteration products in a non-invasive manner has only very recently been demonstrated and makes it a highly relevant technique for the assessment of the chemical condition of works of art.