Method development for binding media analysis in painting cross‐sections by desorption electrospray ionization mass spectrometry

Rationale Art conservation science is in need of a relatively nondestructive way of rapidly identifying the binding media within a painting cross‐section and isolating binding media to specific layers within the cross‐section. Knowledge of the stratigraphy of cross‐sections can be helpful for removing possible unoriginal paint layers on the artistic work. Methods Desorption electrospray ionization mass spectrometry (DESI‐MS) was used in ambient mode to study cross‐sections from mock‐up layered paint samples and samples from a 17th century baroque painting. The DESI spray was raster scanned perpendicular to the cross‐sectional layers to maximize lateral resolution then analyzed with a triple quadrupole mass analyzer in linear ion trap mode. From these scans, isobaric mass maps were created to map the locations of masses indicative of particular binding media onto the cross‐sections. Results Line paint‐outs of pigments in different binding media showed specific and unique ions to distinguish between the modern acrylic media and the lipid‐containing binding media. This included: OP (EO) 9 surfactant in positive ESI mode for acrylic ( m/z 621), and oleic ( m/z 281), stearic ( m/z 283), and azelaic ( m/z 187) acids in negative ESI mode for oil and egg tempera. DESI‐MS maps of mock‐up cross‐sections of layered pigmented binding media showed correlation between these ions and the layers with a spatial resolution of 100 μm. Conclusions DESI‐MS is effective in monitoring binding media within an intact painting cross‐section via mass spectrometric methods. This includes distinguishing between lipid‐containing and modern binding materials present in a known mock‐up cross‐section matrix as well as identifying lipid‐binding media in a 17th century baroque era painting.