Correct identification of pigments and all accompanying phases found in colour layers of historical paintings are relevant for searching their origin and pigment preparation pathways and for specification of their further degradation processes. We successfully applied the analytical route combining non-destructive in situ X-ray fluorescence analyses with subsequent laboratory investigation of micro-samples by optical microscopy, scanning electron microscopy/energy-dispersive spectroscopy and X-ray powder micro-diffraction (micro-XRD) to obtain efficiently all the data relevant for mineralogical interpretations of the copper pigments origin. Cu salts (carbonates, chlorides, sulphates, etc.) used as pigments exist in a range of polymorphs with similar or identical composition. The efficiency of the micro-XRD for direct identification of such crystal phases present in micro-samples of colour layers was demonstrated in the presented paper. A new, until now unpublished, type of copper pigment—cumengeite, Pb21Cu20Cl42(OH)40—used as a blue pigment on a sacral wall painting in the Czech Republic was found by means of micro-XRD. Furthermore, azurite, malachite, paratacamite, atacamite and posnjakite were identified in fragments of colour layers of selected Gothic wall paintings. We found Cu–Zn arsenates indicating the natural origin of azurite and malachite; artificial malachite was distinguishable according to its typical spherulitic crystals. The corrosion of blue azurite to green basic Cu chloride was clearly evidenced on some places exposed to the action of salts and moisture—in a good agreement with the results of laboratory experiments, which also show that oxalic acid accelerates the corrosion of Cu pigments.
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The authors thank restorers Renáta Novotná Zemanová and Pavel Coufal for providing samples and versatile cooperation and Štěpánka Kučková from the Institute of Chemical Technology in Prague for the analyses by MALDI-TOF MS method. This work was supported by the project of the Czech Science Foundation no. 203/07/1324 and by research intentions AV0Z40320502 (Institute of Inorganic Chemistry of the ASCR, v.v.i.) and MSM 6046144603 (Academy of Fine Arts in Prague).
This work was originally presented at the TECHNART 2009—Non-destructive and Microanalytical Techniques in Art and Cultural Heritage, Athens, 27 –30 April 2009
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Švarcová, S., Hradil, D., Hradilová, J. et al. Micro-analytical evidence of origin and degradation of copper pigments found in Bohemian Gothic murals. Anal Bioanal Chem 395, 2037–2050 (2009). https://doi.org/10.1007/s00216-009-3144-7