Review of recent advances on the use of mass spectrometry techniques for the study of organic materials in painted artworks.

The study of painted artworks using scientific methods is fundamental for understanding the techniques used in their creation and their appropriate conservation. The ethical constraints involved in the handling of, and sampling from, these objects has steered recent developments in the field of Heritage science towards a range of new non-invasive/non-destructive spectroscopic techniques capable of providing important insights into their elemental or bulk chemical compositions. Due to the inherent complexities of heritage artefacts, however, their organic components are especially difficult to study in this way and their identification and degradation pathways are thus often best investigated using mass spectrometric (MS) techniques. The versatility, sensitivity and specificity of MS techniques are constantly increasing, with technological advances pushing the boundaries of their use in this field. The progress in the past ten years in the use of MS techniques for the analysis of paint media are described in the present review. While some historical context is included, the body of the review is structured around the five most widely used or emerging capabilities offered by MS. The first pertains to the use of spatially resolved MS to obtain chemical maps of components in cross-sections, which may yield information on both inorganic and organic materials, while the second area describes the development of novel sample preparation approaches for gas chromatography (GC)-MS to allow simultaneous analysis of a variety of components. The third focuses on thermally assisted analysis (either with direct MS or coupled with GC-MS), a powerful tool for studying macromolecules requiring zero (or minimal) sample pre-treatment. Subsequently, the use of soft ionisation techniques often combined with high-resolution MS for the study of peptides (proteomics) and other macromolecules (such as oligosaccharides and triglycerides) is outlined. The fifth area covers the advances in radiocarbon dating of painting components with accelerator MS (AMS). Lastly, future applications of other MS techniques to the study of paintings are mentioned; such as direct analysis in real time MS (DART-MS) and stable isotope ratio MS (IRMS). The latter, having proven its efficiency for the study of lipids in archaeological artefacts, is envisioned to become a valuable tool for this area, whereas DART-MS is already being utilised to study the surface composition of various museum objects. Rapid technological advances, resulting in increased sensitivity and selectivity of MS techniques, are opening up new approaches for paintings analysis, overcoming the fundamental hurdle of sample size available for destructive analysis. Importantly, while the last decade has seen proteomics applications come to the fore, this review aims to emphasise the wider potential of advanced MS techniques for the study of painting materials and their conservation.