Characterization of the deterioration of bone black in the 17th century Oranjezaal paintings using electron-microscopic and micro-spectroscopic imaging techniques

A whitish deterioration product was observed on the dark paint in a number of large-scale oil paintings that are part of the Oranjezaal interior decoration in the Royal Palace Huis ten Bosch (The Hague). The whitened areas of a painting by Pieter Soutman dating from 1648 were micro-sampled and compared with “healthy” black paint using different analytical imaging techniques. The dark paint was identified as bone black in linseed oil with a lead drier added. Microscopic images of the cross-section revealed a white top layer of 10–20 μm in the black paint layer. Imaging the cross-section surface with scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX) and specular reflection Fourier transform infrared (FTIR) showed homogeneous distributions of phosphate, phosphorus and calcium over the black and the white degraded bone black. X-ray diffraction (XRD) showed the presence of calcium phosphate hydrate (Ca3(PO4)2·xH2O), monetite (CaHPO4) with possibly some poorly crystalline or amorphous hydroxyapatite (Ca5(OH)(PO4)3). The EDX maps of lead and carbon, however, showed some discontinuity between the degraded and non-degraded bone black. There was an increase in the lead concentration in the white top layer, and a slight decrease of carbon. Transmission FTIR demonstrated that aromatic network polymers from the carbon black are markedly diminished in the white deterioration product. proposed that the carbonized organic matter in the bone black is vulnerable to photo bleaching in the presence of a lead catalyst under these circumstances.