An evaluation of the impact of urban air pollution on paint dosimeters by tracking changes in the lipid MALDI-TOF mass spectra profile

• New protocol to trace changes in lipid MALDI-TOF-MS profiles of paint dosimeters.
• Optimized Bligh-Dyer method yields higher quality lipid fingerprints from paints.
• Pigments catalyze transesterification processes in the egg yolk lipid fractions.
• New insights into MALDI-TOF-MS analytical study of pigment-binder interactions.

We evaluated the impact of urban air pollution on egg yolk tempera paint dosimeters (binary mixture samples made with historic artist´s blue, red and white pigments) by tracking changes over time in their lipid matrix-assisted laser desorption ionization time-of-flight mass spectra (MALDI-TOF-MS) profiles. We studied triacylglycerols (TGs), phospholipids (PLs) and their oxidation by-products from paint dosimeters that had been exposed outdoors for six months to the polluted atmosphere in the city center of Granada (Spain). Four types of chickens’ eggs were also analyzed to find out whether their lipid mass spectra (lipid fingerprints) varied significantly. The ultimate goal of this research is to provide a precise analytical protocol to show whether the changes in the egg yolk identified in paint dosimeters are due to pigment-binder interactions. The Bligh-Dyer (BD) method was optimized for the extraction of the lipids. This innovative procedure included a washing-step prior to the mass spectrometric analysis, which proved crucial for obtaining higher quality lipid fingerprints. A novel interpretation of the results is proposed by applying the BD method, which suggests that transesterification processes occurred in the lipid fractions that were catalyzed by the pigments in the paint dosimeters. In blank dosimeters specific ions produced by oxidative cleavage of PLs and/or TGs may be used as markers of the presence of egg yolk binders. The composition and structure of the specific lipid compounds are also tentatively proposed. In aged dosimeters the intact content of the TGs and PLs decreased; however, we propose that short-chain oxidative products arising from TGs and PLs are present in all the samples, except for the white lead based dosimeter. We end with a new explanation as to why this dosimeter behaves differently from the others.

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