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Cinnabar alteration in archaeological wall paintings: an experimental and theoretical approach

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Abstract

The red mineral pigment known as cinnabar (HgS) was commonly employed in Roman fresco wall paintings. Fresco artists of the period favored this pigment for its striking red color. However, upon excavation and exposure to air and light, cinnabar-pigmented surfaces recovered from archaeological contexts often proved to be unstable. Mural paintings colored with cinnabar that have been exposed in the open air frequently demonstrate a disfiguring, irreversible darkening of the surface. Traditionally, scholars have attributed this alteration to a light-induced phase change from red α-cinnabar to black β-cinnabar (meta-cinnabar). While this transformation has not been totally excluded, the prevailing view among conservation scientists is that chlorine plays a key role in the darkening process through the formation of light-sensitive mercury chloride compounds, or as a catalyst in the photochemical redox of Hg(II)S into Hg(0) and S(0). Using laboratory-based experiments and thermodynamic modeling, this paper attempts to further clarify the mechanism(s) and kinetics of cinnabar alteration in fresco applications, especially the role of light, humidity, and chlorine ions. Additionally, it explores possible pathways and preventive as well as remedial conservation treatments during or immediately following excavation, to inhibit or retard darkening of cinnabar-pigmented fresco surfaces.

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Notes

  1. The presence of zinc or iron has been shown to reduce the temperature of transformation, to 204 and 305 °C, respectively. While substantially lower, the temperature required to induce this phase change still remains quite high.

  2. While chlorine has been the most thoroughly explored, other halogens, namely iodine, have also been shown to trigger the blackening of cinnabar.

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Acknowledgments

All authors would like to acknowledge Molecular and Nano Archaeology Laboratory at UCLA.

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Authors and Affiliations

  1. UCLA-Getty Conservation Program, University of California, 308 Charles E. Young Drive North, A210 Fowler Building, Los Angeles, 90095, CA, USA

    Madeleine Kegelman Neiman

  2. Department of Materials Science and Engineering, University of California, 410 Westwood Plaza, 2121K Engineering V, Los Angeles, 90095, CA, USA

    Magdalena Balonis

  3. Institute for Technology Advancement, University of California, Engineering VI, Los Angeles, 90095, CA, USA

    Magdalena Balonis

  4. Department of Materials Science and Engineering, University of California, 410 Westwood Plaza, 3111 Engineering V, Los Angeles, 90095, CA, USA

    Ioanna Kakoulli

  5. UCLA/Getty Conservation Program and Cotsen Institute of Archaeology, University of California Los Angeles, 308 Charles E. Young Drive North, A210 Fowler Building, Los Angeles, CA, 90095, USA

    Ioanna Kakoulli

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  1. Madeleine Kegelman Neiman
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Correspondence to Magdalena Balonis.

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Neiman, M.K., Balonis, M. & Kakoulli, I. Cinnabar alteration in archaeological wall paintings: an experimental and theoretical approach. Appl. Phys. A 121, 915–938 (2015). https://doi.org/10.1007/s00339-015-9456-x

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