Artificial orpiment, a new pigment in Rembrandt’s palette

Abstract

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.

Evidence of early amorphous arsenic sulfide production and use in Edo period Japanese woodblock prints by Hokusai and Kunisada

“…4 Raman spectra of (a) the blue areas, (b) the green areas, (c) the dark blue areas and (d) the blue outline of the words in the cartouche in print A, B and C; and (e) dark blue, (f ) the light blue, and (g) the green in print D. Unless orpiment was foreseen, only the 1550-2600 cm −1 region of the Raman spectra was measured as characteristic contributions for both indigo and Prussian blue are found in this region. In Raman spectroscopy, the contributions observed between 100 and 600 cm −1 correspond to natural arsenic sulfide in prints by Hokusai (A-C) and to artificial arsenic sulfide in the print by Kunisada (D); the one at 1573 indicates indigo and the pair of contributions between 2095 and 2155 cm −1 correspond to Prussian blue profile and particular contributions are characteristic for the various bending and stretching bonds found in amorphous arsenic sulfide pigments, as reported in previous arsenic sulfide characterization studies [14,22,23]. While not previously reported as a characteristic for amorphous arsenic sulfide pigments, the increase in the 100-250 cm −1 region has consistently been noted in non-background corrected spectra in identification studies of amorphous arsenic sulfide pigments [8,10,14,20,22].…”

Imaging secondary reaction products at the surface of Vermeer’s Girl with the Pearl Earring by means of macroscopic X-ray powder diffraction scanning

“…2, 4). Palmierite has previously been identified as an alteration product in paint fragments from seventeenth-century Dutch paintings by Johannes Vermeer, Jacob Jordaens and Rembrandt, and the authors have also identified it in paintings by Jan Steen, Martinus Nellius and Jan Davidsz de Heem [20,[29][30][31][32][33]. Anglesite has previously been found on an ancient bronze inkwell and in paintings by Van Gogh and Memling [34][35][36].…”

Insights into the composition of ancient Egyptian red and black inks on papyri achieved by synchrotron-based microanalyses

“…Its distribution cannot be associated to a specific color and it may be present as a transparent film. Indeed, various lead sulfatespalmierite but also anglesite (PbSO 4 ) and lanarkite [Pb 2 (SO 4 ) O]-have already been reported as degradation products in paintings, where they usually form a transparent film and sometimes protrusions (43)(44)(45)(46). They were detected in Old Master Paintings and associated with colored pigments (e.g., smalt and lakes) in combination with lead white that is present in the same or an adjacent paint layer.…”