Tracking the transformation and transport of arsenic sulfide pigments in paints: synchrotron-based X-ray micro-analyses†
Realgar and orpiment, arsenic sulfide pigments used in historic paints, degrade under the influence of light, resulting in transparent, whitish, friable and/or crumbling paints. So far, para-realgar and arsenic trioxide have been identified as the main oxidation products of arsenic sulfide pigments. This paper shows that after photo-degradation, various oxidation and migration processes take place. Synchrotron radiation (SR) micro-X-ray fluorescence (μ-XRF) reveals arsenic to be distributed throughout the whole multi-layered paint system. Arsenic (As) K-edge micro-X-ray absorption near edge structure (μ-XANES) analyses indicate the presence of an intact AsxSy pigment, arsenite compounds (As3+; As2O3), and arsenate compounds (As5+); the latter are certainly present as calcium, lead, aluminium and iron arsenates. Sulfur (S) K-edge μ-XANES points to the conversion of the sulfide (S2−) group to a sulfate (SO42−) group, probably via an elemental sulfur (S0) or sulfoxide (S2+) compound. Principal Component Analysis (PCA) and subsequent k-means clustering of multi-energy SR μ-XRF maps and μ-XANES were performed to identify the various arsenic species and visualize their distribution. The arsenates (As5+) are spread throughout the entire paint system and dominate the photo-degraded paint and ground layers, while the arsenite compounds (As3+) are located close to the intact arsenic sulfide pigment. The oxidation of arsenic trioxide into arsenates likely takes place in aqueous solutions. The presence of As5+ compounds in the paint systems indicates that the arsenic trioxide is dissolved by ambient water present in the paint. Arsenite and arsenate compounds are water soluble and are transported by water throughout the paint system. This knowledge is crucial for the conservation field, as this is the first time that (indirect) evidence of water transport within paintings has been given.
- This article is part of the themed collection: Synchrotron radiation and neutrons in art and archaeology