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Precise and Accurate Analysis of Gold Alloys: Varna, the Earliest Gold of Mankind—A Case Study

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Recent Advances in Laser Ablation ICP-MS for Archaeology

Part of the book series: Natural Science in Archaeology ((ARCHAEOLOGY))

Abstract

During the last decade an analytical routine was established that allows determining the composition of gold artifacts for major and trace elements by LA-ICP-MS. This micro-invasive method has proven highly suitable for detailed characterization of prehistoric gold in order to investigate its chaîne opératoire. At the CEZA laboratory (Mannheim, Germany) two different analytical set-ups were developed that yielded accurate and precise results for determining the whole range of matrix components within the gold. They are based upon different calibration strategies—liquid calibration with the ICP-MS operating under wet plasma conditions, and external calibration by solid standard reference materials with the ICP-MS operating under dry plasma conditions—that enable flexible adjustment according to different sample properties. They are described and compared within this paper. An archaeological case study of gold finds from the chalcolithic cemetery of Varna (Bulgaria) demonstrates the applicability of the analytical methods for archaeometallurgical studies. These analyses yielded valuable information for defining and comparing groups of gold artifacts that allude to their distribution within the burial site. However, the comparison of artifact gold with geological gold samples proved problematic, and clear relations between artefacts and specific gold occurrences are difficult to demonstrate.

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Notes

  1. 1.

    These projects examined Early Bronze Age gold on the Nebra Sky Disc (Germany), Peruvian gold, and gold items from the Copper Age cemetery at Varna (Bulgaria), gold from Cambodia, and recently, early Iron Age gold from Germany and France (Schlosser et al. 2009, 2012; Ehser et al. 2011; Pernicka 2014b).

  2. 2.

    LA-ICP-MS is also being used to study the production and provenance of prehistoric iron (Brauns et al. 2013; Leroy et al. 2011).

  3. 3.

    These settings were empirically determined to be most suitable for the precise, accurate and reproducible measurement of gold. Depending on the sample’s properties (e.g. size and thickness) these settings must be adjusted. Other materials require different settings.

  4. 4.

    The interactions between laser and sample are complex and still a matter of investigation (Durrant 1999; Cromwell and Arrowsmith 1995).

  5. 5.

    The analyses were performed within a bilateral project between German and Bulgarian research institutions and universities. The project focuses on the culture historic investigation of the Varna cemetery and is financed by the German Research Foundation (DFG). For further information about the site see: Fol and Lichardus (1988); Echt et al. (1991); Hansen (2009); Krauß (2010); Todorova (1991); Lichardus (1991).

  6. 6.

    Small shavings from a representative sample of objects were taken at the Museum of National History in Sofia and the Historical Regional Museum in Varna by Kalin Dimitrov (Archaeological Institute of the Bulgarian Academy of Sciences).

  7. 7.

    This assumption is based on the analytical observations of low copper and trace element concentrations that are in agreement with what we know about the composition of natural gold. There is for the most part no clear analytical indication for intentional alloying with copper and/or silver. However, the mixing of gold from different origins cannot be excluded.

  8. 8.

    In this context it is noteworthy that all analysed objects can be confirmed as having been cast. In the literature about early gold working it is often assumed that “in the very beginning of handling gold it was most likely completely or partially sintered and never really melted” (Raub 1995: 243) and that “[a]lthough copper was frequently cast, this technique was hardly ever used for gold.” (Eluère 1989: 37). Based on our new analyses (that also comprise technological examinations) these assumptions can be dismissed.

  9. 9.

    Recent investigations of placer gold conducted at the CEZA demonstrate this inhomogeneous character very clearly.

  10. 10.

    A. Schmiderer was able to integrate about 150 gold occurrences from the alpine region, the Carpathians, the Czech Republic, and the German regions of Thuringia and Saxony in his PhD study of the possible gold sources used to produce the Nebra Disc.

  11. 11.

    A. Ehser was able to prospect occurrences in Romania and the Balkans as well as in southwestern Europe (Spain, Portugal and the UK).

  12. 12.

    Except for piles of river sediment, which are usually difficult to date, there are hardly any archaeological traces of this activity.

  13. 13.

    One has to reckon as well with changes in the geochemical structure over time as placers are “dynamic“ systems that are impacted by numerous environmental influences.

  14. 14.

    Personal information by Danail Yovchev. Until quite recently information about Bulgarian gold deposits was difficult to access. “Due to the restrictive information policy of the Bulgarian government […] only limited information was [adapted by the author] available on Bulgarian gold deposits.” (Lehrberger 1995: 137).

  15. 15.

    This is the topic of a PhD thesis by Danail Yovchev at the Geological Department of Sofia University (supervisor: Prof. Veselin Kovachev).

  16. 16.

    “Geologically, economic concentrations of gold and platinum-group metals do not occur in the same primary deposit types but, rather, are found independently from each other in different environments. While platinum-group deposits are restricted to magmatic processes (e.g., layered intrusions), gold deposits are formed by hydrothermal processes […]. Therefore, platinum or platinum-group metals in gold objects are interpreted as indicators for placer gold deposits in which the tributaries collected gold and platinum from both mineralization styles.” (Junk and Pernicka 2003: 314).

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Acknowledgements

The studies of the gold finds from Varna were funded by the German Research Foundation (DFG, Pe 405-25) and are the subject of a PhD thesis (Verena Leusch). For their co-operation and help in sampling we sincerely thank Ivelin Kuleff (Chemical Institute, Sofia University), Raiko Krauß (University Tübingen), Vladimir Slavchev, Olga Pelevina (Historical Regional Museum in Varna), Kalin Dimitrov (Archaeological Institute of the Bulgarian Academy of Sciences) and Svetla Tsaneva (Museum of National History in Sofia). Special thanks go to Barbara Armbruster (CNRS, Toulouse), who provided us with valuable photos and information about the production technology of prehistoric gold. The integration of the latest geological information was only possible due to the dedicated research of Danail Yovchev and Veselin Kovachev (Geological Institute, Sofia University). Furthermore, the authors want to thank Nicole Lockhoff, Ursula Rothe and René Kunze for improving the language of this paper, and for helpful discussions. Finally, we would like to thank two anonymous reviewers for their helpful comments.

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  1. Curt-Engelhorn-Zentrum Archäometrie, D6 3, 68159, Mannheim, Germany

    Verena Leusch, Michael Brauns & Ernst Pernicka

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  1. Verena Leusch
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  2. Michael Brauns
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  3. Ernst Pernicka
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Correspondence to Verena Leusch .

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Editors and Affiliations

  1. Integrative Research Center, Elemental Analysis Facility, Field Museum of Natural History, Chicago, Illinois, USA

    Laure Dussubieux

  2. Department of Anthropology, University of Notre Dame, Notre Dame, Indiana, USA

    Mark Golitko

  3. Institut de Recherche sur les Archéomatériaux Centre Ernest Babelon, CNRS/Université d’Orléans, Orléans, France

    Bernard Gratuze

Appendix

Appendix

Table 7.7 Composition of the in-house SRMs NA1 and NA2, the NIST standards FAU 7 and FAU 10
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Table 7.8 Standard solutions
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Table 7.9 List of measured elements (isotopes), dwell time, resolution (settings of the ICP-MS) and mean LOD (calculated for dry plasma conditions; estimated values italicised)
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Leusch, V., Brauns, M., Pernicka, E. (2016). Precise and Accurate Analysis of Gold Alloys: Varna, the Earliest Gold of Mankind—A Case Study. In: Dussubieux, L., Golitko, M., Gratuze, B. (eds) Recent Advances in Laser Ablation ICP-MS for Archaeology. Natural Science in Archaeology. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-49894-1_7

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