"Naples yellow-containing oil paints aged under natural and artificial conditions were investigated as model systems to evaluate the potential of secondary ion mass spectrometry (SIMS) when used in combination with other mass spectrometric and spectroscopic analytical methods. Although the advantage of SIMS is the simultaneous detection of organic and inorganic components and their spatial distribution, the methodology has limitations in compound sensitivity and shows bias towards certain constituents. Gas chromatography-mass spectrometry (GC/MS) shows dicarboxylic fatty acids to be main components in the paint, but SIMS detects these compounds poorly. Electrospray ionisation mass spectrometry (ESIMS) shows a broad range of glyceryl derivatives of mono- and dicarboxylic fatty acids (mono-, di- and triglyceride derivatives), while SIMS only detects the mono- and diglycerides of the monocarboxylic acids. Compared to SIMS, direct temperature-resolved mass spectrometry (DTMS) offers greater insight into how the various constituents are incorporated into the paint film, but SIMS data supports the information provided by Fourier transform infrared (FTIR) on metal soap formation. The surface sensitivity of SIMS is an advantage for probing paint constituent distributions and was exploited to examine variations in the composition of the top and bottom of a paint film, and the spatial correlation between metal and fatty acid composition in metal soap aggregates. Disadvantages of SIMS are the low yields and matrix dependency of the organic species in the paint matrix. Application of an ultra-thin gold coating overcomes this, and

Int. J. Mass Spectrom.

Keune, K., Boon, J. J., Peggie, D., & Higgitt, C. (2009). "Evaluation of the ""added value"" of SIMS : a mass spectrometric and spectroscopic study of an unusual Naples yellow oil paint recontruction". Int. J. Mass Spectrom., 284, 22–34. doi:10.1016/j.ijms.2008.10.016