Over the past several decades the painting An Old Man in Military Costume by Rembrandt Harmensz van Rijn (ca. 1630–31; J. Paul Getty Museum, 78.PB.246) has been the subject of a number of investigations carried out in order to better visualize a second painting beneath the surface figure. The underlying image–the head and shoulders of a man wearing a cloak–is oriented 180 degrees from the upper image and appears to be fairly complete. Scanning macro x-ray fluorescence (XRF) spectroscopy reveals the face is painted with lead white and a mercury-containing pigment (likely vermilion), and the cloak is painted with a copper-containing pigment. Following the revelation and digital color reconstruction of the underlying figure, a number of questions still remained. Here, through the use of infrared reflectance imaging spectroscopy (i.e., hyperspectral imaging) and macro-XRF imaging spectroscopy, together with cross-sections taken from targeted areas, the sequence of painting in both compositions was explored. Of particular interest was the discovery of evidence of multiple attempts to situate the lower figure, and the subsequent application of a blocking-out layer over the lower figure before the artist rotated the panel and executed the upper figure. In addition, examination of the placement of the two images on the panel adds to our understanding of the subtle complexities of Rembrandt's working process.

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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.

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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