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Laser ablation-ICP-MS depth profiling to study ancient glass surface degradation

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Abstract

In general the analysis of archeological glass represents a challenge for a wide variety of objects because of the presence of physical and/or chemical damage on the surface of the artifact, also known as weathering or corrosion. To retrieve accurate bulk elemental information by laser ablation-inductively coupled plasma-mass spectrometry (ICP-MS), the original, pristine glass needs to be “reached”, thereby penetrating the alteration layer which is often more than 10 μm thick. To study this alteration layer the laser was operated in the drilling mode, either with a low (1 Hz) or a high (10 Hz) pulse repetition rate for a period of 50 s yielding detailed spatial information for ca. 20 elements over a shallow depth (ca. 5 μm) or less-detailed spatial information for 50–60 elements over a greater depth (ca. 50 μm). Quantitative elemental depth profiles (in wt%) were obtained with the so-called sum normalization calibration protocol, based on summation of the elements as their oxides to 100 wt%. We were able to associate the increase of SiO2 (in wt%) in the alteration layer to the volumetric mass density change in the glass as a result of depletion of Na2O and K2O. Also the interaction of the number of laser shots with the alteration layer is shown experimentally via depth measurements using profilometry. Chemical and physical changes in four ancient glass artifacts, directly and indirectly measureable by laser drilling, were studied as a function of internal and external factors such as age, composition, and exposure conditions.

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Acknowledgments

The authors would like to thank Dr. Nicole Boivin and coworkers (Sealinks project) and Dr. Edward Pollard (British Institute in Eastern Africa) for making the African glass beads available, the Corning Museum of Glass (via Professor Norman Tennent) for providing the crizzled glass, Professor Elti Cattaruzza (University Ca’ Foscari of Venice, Italy) for optical surface profiling analysis, and Dr. Marilee Wood (University of the Witwatersrand, South Africa), Professor Peter Robertshaw (California State University, USA), and Stephen Koob (Corning Museum of Glass) for constructive discussions in the preparation of this manuscript.

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Authors and Affiliations

  1. Analytical Chemistry Laboratory, National Institute of Chemistry, Hajdrihova 19, 1000, Ljubljana, Slovenia

    Serena Panighello & Johannes T. Van Elteren

  2. Department of Molecular Sciences and Nanosystems, Ca’ Foscari University of Venice, Calle Larga Santa Marta 2137, 30123, Venice, Italy

    Serena Panighello, Emilio F. Orsega & Ligia M. Moretto

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  1. Serena Panighello
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  2. Johannes T. Van Elteren
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  3. Emilio F. Orsega
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  4. Ligia M. Moretto
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Correspondence to Johannes T. Van Elteren.

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Panighello, S., Van Elteren, J.T., Orsega, E.F. et al. Laser ablation-ICP-MS depth profiling to study ancient glass surface degradation. Anal Bioanal Chem 407, 3377–3391 (2015). https://doi.org/10.1007/s00216-015-8568-7

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  • DOI: https://doi.org/10.1007/s00216-015-8568-7

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