Macroscopic x-ray fluorescence imaging spectroscopy (MA-XRF) and reflectance imaging spectroscopy (RIS) are important tools in the analysis of cultural heritage objects, both for conservation and art historical research purposes. The elemental and molecular distributions provided by MA-XRF and RIS respectively, are particularly useful for the identification and mapping of pigments in easel paintings. While MA-XRF has relatively established data processing methods based on modeling of the underlying physics, RIS data cannot be modeled with sufficient precision and its processing has considerable room for improvements. This work seeks to improve RIS data processing workflows in the short wavelength infrared range (SWIR, 1000–2500 nm) with a novel method that fits Gaussian profiles to pigment-specific absorption features, and we compare its performance to MA-XRF for the task of semi-quantitative pigment mapping, evaluating their limits of detection (LODs) and the matrix effects that affect their signals. Two pigments are considered in this work, lead white and blue verditer, which are mapped in SWIR RIS using the first overtone of -OH stretching of their primary compounds, hydrocerussite (Pb₃(CO₃)₂(OH)₂) and azurite (Cu₃(CO₃)₂(OH)₂), at 1447 and 1497 nm respectively, and in MA-XRF using the Pb-L and Cu-K fluorescence signals. The methods are evaluated using two sets of custom-prepared paint samples, as well as a 16th-century painting, discussing the identification, mapping, and semi-quantitative analysis of the considered pigments. We found SWIR RIS to be a pigment-specific method with a longer linear range but inferior LODs and penetration depth when compared to MA-XRF, the latter is often not capable of discriminating between different pigments with identical elemental markers. We furthermore present a novel color scale that allows the simultaneous visualization of signals above and below a confidence limit.

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.

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)’.

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.

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.

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.

This study introduces the use of macroscopic X-ray fluorescence (MA-XRF) for the detection, classification and imaging of forensic traces over large object areas such as entire pieces of clothing and wall paneling. MA-XRF was sufficiently sensitive and selective to detect human biological traces like blood, semen, saliva, sweat and urine on fabric on the basis of Fe, Zn, K, Cl and Ca elemental signatures. With MA-XRF a new chemical contrast is introduced for human stain detection and this can provide a valuable alternative when the evidence item is challenging for conventional techniques. MA-XRF was also successfully employed for the chemical imaging and classification of gunshot residues (GSR). The full and non-invasive elemental mapping (Pb, Ba, Sr, K and Cl) of intact pieces of clothing allows for a detailed shooting incident reconstruction linking firearms and ammunition to point of impact and providing information on the shooting angle. In high resolution mode MA-XRF can even be used to provide information on the shooting order of different ammunition types. Finally, by using the surface penetration of X-rays we demonstrate that the lead signature of a bullet impact can be easily detected even if covered by multiple layers of wall paint or human blood.