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Trace elements in natural azurite pigments found in illuminated manuscript leaves investigated by synchrotron x-ray fluorescence and diffraction mapping

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Abstract

We present trace-element and composition analysis of azurite pigments in six illuminated manuscript leaves, dating from the thirteenth to sixteenth century, using synchrotron-based, large-area x-ray fluorescence (SR-XRF) and diffraction (SR-XRD) mapping. SR-XRF mapping reveals several trace elements correlated with azurite, including arsenic, zirconium, antimony, barium, and bismuth, that appear in multiple manuscripts but were not always detected by point XRF. Within some manuscript leaves, variations in the concentration of trace elements associated with azurite coincide with distinct regions of the illuminations, suggesting systematic differences in azurite preparation or purification. Variations of the trace element concentrations in azurite are greater among different manuscript leaves than the variations within each individual leaf, suggesting the possibility that such impurities reflect distinct mineralogical/geologic sources. SR-XRD maps collected simultaneously with the SR-XRF maps confirm the identification of azurite regions and are consistent with impurities found in natural mineral sources of azurite. In general, our results suggest the feasibility of using azurite trace element analysis for provenance studies of illuminated manuscript fragments, and demonstrate the value of XRF mapping in non-destructive determination of trace element concentrations within a single pigment.

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Acknowledgements

The authors thank Prof. Adam Smith and the Cornell University Landscapes and Objects Laboratory for the use of the pXRF system. The authors also thank the Cornell Library Conservation Laboratory for assistance preparing custom mounts for synchrotron measurements of the manuscript fragments. The authors are grateful to Mr. Frederik Vanmeert for his generous tutorial guidance in using XRDUA software, to Dr. Catherine Patterson for helpful conversations, and to Prof. Andrew Hicks and Prof. Nigel Palmer for offering their invaluable expertise. This work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS) which is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-1332208.

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Authors and Affiliations

  1. Wilson Laboratory, Cornell High Energy Synchrotron Source, Ithaca, NY, 14853, USA

    Louisa M. Smieska & Arthur R. Woll

  2. Medieval Studies Program, Cornell University, Goldwin Smith Hall, Ithaca, NY, 14853, USA

    Ruth Mullett

  3. Cornell Library Rare and Manuscript Collections, Cornell University, Ithaca, NY, 14853, USA

    Laurent Ferri

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  1. Louisa M. Smieska
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Correspondence to Louisa M. Smieska.

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Smieska, L.M., Mullett, R., Ferri, L. et al. Trace elements in natural azurite pigments found in illuminated manuscript leaves investigated by synchrotron x-ray fluorescence and diffraction mapping. Appl. Phys. A 123, 484 (2017). https://doi.org/10.1007/s00339-017-1093-0

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