This paper reports on how the application of macro X-ray fluorescence (MA-XRF) imaging, in combination with the re-examination of existing paint cross-sections, has led to the discovery of a new pigment in Rembrandt’s palette: artificial orpiment. In the NWO Science4Arts ‘ReVisRembrandt’ project, novel chemical imaging techniques are being developed and applied to the study of Rembrandt’s late paintings in order to help resolve outstanding questions and to gain a better understanding of his late enigmatic painting technique. One of the selected case studies is the Portrait of a Couple as Isaac and Rebecca, known as ‘The Jewish Bride’, dated c. 1665 and on view in the Rijksmuseum. During the re-installation of the Rijksmuseum in 2013, the picture was scanned using the Bruker M6 Jetstream MA-XRF scanner. The resulting elemental distribution maps made it possible to distinguish many features in the painting, such as bone black remains of the original hat (P, Ca maps), and the now discolored smalt-rich background (Co, Ni, As, K maps). The arsenic (As) map also revealed areas of high-intensity in Isaac’s sleeve and Rebecca’s dress where it could be established that it was not related with the pigment smalt that also contains arsenic. This pointed to the presence of a yellow or orange arsenic-containing pigment, such as realgar or orpiment that is not associated with the artist’s palette. Subsequent examination of existing paint cross-sections from these locations taken by Karin Groen in the 1990s identified isolated, almost perfectly round particles of arsenic sulfide. The round shape corresponds with published findings on a purified form of artificial orpiment glass obtained by dry processing, a sublimation reaction. In bright field, the particles characteristically exhibit a dark cross in the middle caused by internal light reflections. The results of additional non-invasive techniques (portable XRD and portable Raman) are discussed, as well as the implications of this finding and how it fits with Rembrandt’s late experimental painting technique.@en

The assessment of the structural condition of cultural heritage objects is important for conservation interventions and their long-term preservation. This investigation concerns The Night Watch (1642), a large-format 17th-century canvas painting by Rembrandt van Rijn that is on display in the Rijksmuseum, Amsterdam. This painting, which has a complex treatment history, has various damaged areas and has undergone three wax-resin relinings. In 1975 the canvas was slashed twelve times with a serrated dinner knife, including several long slashes in the area of Captain Frans Banninck Cocq’s breeches. In 2021, prior to a proposed new structural intervention involving retensioning of the canvas, it was important to evaluate the structural condition of the repaired slashes and of another repair, specifically an old canvas insert in the drum. For this, an in-situ inspection was carried out in the Rijksmuseum as a part of Operation Nightwatch. 3D shearography instrument with thermal loading was used to inspect these two areas of interest on the reverse of The Night Watch. The results showed that the out-of-plane strain in the breeches does not show any large deviations, which alleviated conservators’ concerns about the adhesion of the lining canvas and stability of previous repairs in this region. The patch in the drum showed higher out-of-plane strain variations. This was explained by the lower quality of the patched canvas compared to the repaired slashes in the breeches of Banninck Cocq. Overall, 3D shearography provided valuable inspection results for assurances regarding the structural integrity of the 1975 repairs and the wax-resin lining in The Night Watch, reducing the risks and providing the confidence to proceed with the planned retensioning of the canvas.@en

Late paintings of Rembrandt van Rijn (1606–1669) offer intriguing problems for both art historians and conservation scientists. In the research presented here, the key question addressed is whether observed stylistic differences in paint handling can be correlated with material differences. In Saul and David, in the collection of the Royal Picture Gallery Mauritshuis in The Hague, NL, the stylistic differences between the loose brushwork of Saul’s cloak and the more detailed depiction of his turban and the figure of David have been associated with at least two painting stages since the late 1960s, but the attribution of each stage has been debated in the art historical literature. Stylistic evaluation of the paint handling in the two stages, based on magnified surface examination, is further described here. One of the research goals was to determine whether the stylistic differences could be further differentiated with macroscale and microscale methods of material analysis. To address this, selected areas of the painting having pronounced stylistic differences were investigated with two macroscopic chemical imaging methods, X-ray fluorescence and reflectance imaging spectroscopies. The pigments used were identified and their spatial distribution was mapped. The mapping results show that the passages rendered in more detail and associated stylistically with the first painting stage, such as the orange-red color of David’s garment or the Greek key design in Saul’s turban, were painted with predominately red ochre mixed with vermilion. The regions of loose, bold brushwork, such as the orange-red slashing strokes in the interior of Saul’s cloak, associated with the second painting stage, were painted with predominately red ochre without vermilion. These macroscale imaging results were confirmed and extended with scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM–EDX) analysis of three cross-sections taken from regions of stylistic differences associated with the two painting stages, including one sample each from the right and left sleeve of David, and one from the interior of Saul’s cloak. SEM–EDX also identified a trace component, barium sulfate, associated with the red ochre of the second stage revisions. Combining mapping information from two spectroscopic imaging methods with localized information from microscopic samples has clearly shown that the stylistic differences observed in the paint handling are affiliated with differences in the chemical composition of the paints.[Figure not available: see fulltext.].@en

Recent macro-XRF scanning of Rembrandt’s Selfportrait from 1669 in the Mauritshuis – as part of the ReVisRembrandt project – has revealed significant new information about the pigments and build-up of the painting. The elemental distribution maps make clear that the umber-rich ground plays a very important role in the final appearance of this painting, information that is highly relevant for the study of this self-portrait, as well as many other late Rembrandt paintings. It was also possible and infrared imaging, it is anticipated macro-XRF scanning will become an important diagnostic tool for conservators and art historians alike. to image the presence of organic lakes (by means of the potassium map) and bone black (by means of the calcium and phosphorus maps) in the upper paint layers. In addition to conventional investigative techniques, such as x-radiography and infrared imaging, it is anticipated macro-XRF scanning will become an important diagnostic tool for conservators and art historians alike.@en

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. @en

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. @en