Hyperne Interactions 150: 15, 2003. 2003 Kluwer Academic Publishers. Printed in the Netherlands.

Material Analysis in Archaeology

R. GEBHARD
Archologische Staatssammlung Mnchen, Lerchenfeldstrae 2, 80538 Mnchen, Germany Abstract. Material nds are the main source of archaeological knowledge. The scientic analysis of found objects can help to interpret many aspects of archaeological interest, like production and manufacturing processes or provenance. Such insights can often be used in further historical interpretations. Key words: material analysis, archaeology, physical methods, Mssbauer spectroscopy.

1. Introduction The term archaeology is generally used for a special part of the historic sciences. Archaeology tries to reconstruct the culture and history of past societies, especially of those on which no or poor written sources exist and for which information on every day life is scarce. Archaeology, in its broadest sense, studies a past material culture. In detail it is like a puzzle of very different aspects that is tted together to a picture of the past. Archaeology today uses a whole variety of methods and tools: survey and excavation, environmental analysis with pollen or glacial records, paleobotany and paleozoology, scientic and historical dating methods, historic and iconographic sources, models that were developed from sociology and ethnology, archaeological experiments and, last but not least, material analysis of found artefacts [1]. The use of methods borrowed from the natural sciences is nowadays subsumed under the term archaeometry. 2. Material analysis and technological studies Material analysis plays a dominant role in archaeometry. As manifold as the applied methods are, as different may be the results. The application of only one method is often not enough, and only the application of different methods may result in a detailed view of the objects. Material analysis has two main topics: the characterisation of the material of which objects consist and the characterisation of the technical treatment or the manufacturing of the objects. The rst can, for instance, give information about the provenance of the material, while the latter helps to reconstruct ancient techniques. The provenance of an object or its raw material can give information about resources, trade contacts and economic systems. The ancient techniques used in

R. GEBHARD

a culture can be a main argument in the discussion of the level of civilisation the culture has. In most cases, highly developed techniques only appear in complex, structured social systems, because experiments and communication between different crafts result in technical progress. The application of scientic analysis in the second half of the 20th century has brought new light into archaeology. Today material analysis is an integral part of the archaeological work. The secret of success in such interdisciplinary studies is always a very close collaboration between archaeologists and scientists. It is therefore necessary that both be familiar with the principles of the methods used.

3. Analysis of ring techniques by Mssbauer spectroscopy Processes in which high temperatures were used are of special interest in studies of ancient technologies. The quality of ceramic production or metal working depends on the available ring techniques. Two aspects have to be monitored during a ring process: the temperature and the kiln atmosphere. Only a perfect control of both can result in a high-quality product. The experience of the craftsmen was widely different in different prehistoric cultures. It depended on the traditions that existed in the society. Smiths, for instance, often represent a very small community with jealously guarded trade secrets. Their work was often highly specialized and enabled them to live without additional farming. Pottery making, on the other hand, was a part of everyday life in many prehistoric cultures. Generally, however, in highly developed cultures pottery making and other crafts tended to specialise, and often the products and techniques became standardised. The changes in the skills of crafts are of much interest for the archaeologist, since they can give information on internal technical developments or inuences from outside. In this context, processes requiring temperatures near 1000 C are of special interest since such temperatures are difcult to reach and control [2]. Much experience in constructing kilns as well as a thorough knowledge of the properties of the fuel are needed. The command of temperature is essential in the development of metallurgy, of glass making and, though to a lesser extent, of pottery. The introduction of charcoal as a fuel in the bronze age went along with enforced ventilation of res by bellows. This was denitely an evolution that accompanied the spreading of techniques for the melting of ores. At the same time, kiln and furnace linings began to be used to restrict the loss of heat and to improve the possibility to control the atmosphere of the re. Mssbauer spectroscopy on 57 Fe has turned out to be one of the best methods for technological studies of ring techniques [3]. It can be applied to all ironcontaining materials involved in the ring process. Typical objects that can be studied by Mssbauer spectroscopy are all kinds of ceramics, like pottery, tuyeres, moulds and parts of furnaces, as well as non-ceramic materials like slags and glass. Mssbauer measurements on red ceramic materials contain information on ring temperatures, kiln atmospheres and even complex ring cycles. For an in-

MATERIAL ANALYSIS IN ARCHAEOLOGY

terpretation a comparison with measurements of material red under controlled conditions in the laboratory is often necessary. At this point the potential of the method can best be illustrated by an example: In Celtic Europe the adoption of a monetary system was essential for the establishment of a specialised economy. Gold, silver and bronze coins were used in internal and external trade. The coins were produced in a standardised process [4]. For silver and gold coins, blanks of the desired weight were produced rst and minted afterwards with dies. The blanks for gold coins were melted in clay moulds, which were used only once. This facilitates an exact reconstruction of the melting process by Mssbauer measurements on different layers of the moulds [5, 6]. By comparison with samples subjected to laboratory ring under controlled conditions, the Mssbauer measurements gave three results: (i) The vitried surface was heated to temperatures above 1050 C, which are required for melting gold. (ii) The temperature of the bottom and the interior of the coin mould never exceeded 500700 C, and (iii) the melting process took place in a reducing atmosphere. As the distance from the top to the interior of the moulds is less than a centimeter, the ring can have lasted only for a short time and the heat must have been applied from the top. These notions obtained from the Mssbauer analysis were used in conducting a eld test in a reconstructed furnace. Embedded thermocouples in the replica coin moulds used in the eld experiment exactly reproduced the conclusions from Mssbauer spectroscopy. Only the uppermost layer of the coin moulds attained temperatures above 1000 C while the core was heated to between 400 and 800 C. The melting point of gold was reached after 2 to 5 minutes. On the other hand, coin moulds from Southern England show uniform ring in a reducing atmosphere, thus telling us that they were used in a different manner [7]. 4. Pottery analysis In the same way as Mssbauer spectroscopy was applied in this example, it can be used in pottery analysis [8, 9]. During a project dealing with a certain culture, one normally studies a number of different materials, which exhibit a variety of Mssbauer spectra. This can have different reasons, e.g., variations in the clay sources, different techniques used by different people or chronological differences. The interpretation often requires a rather large number of sherds to be analysed. We have observed that only when several dozens of samples have been studied by Mssbauer spectroscopy it becomes possible to group the spectra into types. Such types may represent standard production procedures used, for instance, in certain workshops. 5. Analysis of non-ceramic material Besides ceramics, Mssbauer spectroscopy allows one to study many other materials, like glass, gold, iron, slags, or phenomena like the corrosion of metals

R. GEBHARD

and the weathering of non-metals. In glass studies, Mssbauer spectroscopy gives information on the chemical state of the iron that is present in quantities up to about a percent in most antique glasses [10]. Mssbauer spectroscopy can also be used to study the chemical state of tin and antimony in glasses or glazes [11]. The colour of glass is mainly caused by metal compounds added to the glass. It depends on the oxidation state of the metal ions and various factors like the glass composition and the kiln atmosphere. Mssbauer spectroscopy can give detailed information on some of these features. Mssbauer spectroscopy of gold is a useful supplement for other analytical techniques. As precious objects from museums normally cannot be sampled, nondestructive analytical techniques are required. These, however, give only the composition of the outer surface that can be altered during burial. The same is true for gamma ray backscattering and CEMS Mssbauer spectroscopy, although these methods allow to probe different depths, while transmission Mssbauer spectroscopy can give information on the bulk of the gold objects [3, 12, 13]. The analysis of slags is always important for the reconstruction of the metal melting process and metal production [14]. Mineral phases in the slags can easily be identied by Mssbauer spectroscopy and can be used to give information on the furnace temperatures and atmospheres used during the melting process.

6. Corrosion studies Another point that should be mentioned here is the study of corrosion. This may become a major application for Mssbauer spectroscopy in the future, since corrosion studies are very important for restoration concepts of both metallic and non-metallic objects. Many restoration departments of museums have still no possibility of getting the necessary information on the chemical processes leading to surface corrosion of iron artefacts that they need for an adequate treatment and for conservation. Iron Mssbauer spectroscopy could be developed to a powerful and relatively cheap routine method in this eld.

7. Conclusions Material analyses and especially Mssbauer spectroscopy today can answer or at least help to answer a wide variety of archaeological questions. It should, however, not be forgotten that it is not only the scientic aspect that should provoke an archaeologist, and a scientist to analytical investigations. It is as well the commitment to better understand the beautiful objects produced by our ancestors and to conserve the material objects of our cultural heritage for the next generation. In this sense Mssbauer spectroscopy will keep its conservative place.

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References
1. 2. Renfrew, C. and Bahn, P. G., Archaeology: Theory, Methods and Practice, 3rd edn, Thames and Hudson, New York, 2000. Gebhard, R., Industry in Celtic Oppida Aspects of High Temperature Processes, In: G. Morteani and J. P. Northover (eds.), Prehistoric Gold in Europe: Mines, Metallurgy and Manufacture, Vol. 280 of NATO ISI Series E: Applied Sciences, Kluwer Academic Publishers, Dordrecht, 1995, pp. 261272. Wagner, F. E. and Kyek, A., Mssbauer Spectroscopy in Archaeology: Introduction and Experimental Considerations, In: U. Wagner (ed.), Mssbauer Spectroscopy in Archaeology, Hyp. Interact., topical issue, Vol. I, to be published. Moesta, H. and Franke, P. R., Antike Metallurgie und Mnzprgung. Ein Beitrag zur Technikgeschichte, Birkhuser Verlag, Basel, 1995. Gebhard, R., Groe, G., Lehrberger, G., Riederer, J., Wagner, F. E. and Wagner, U., What Mssbauer Spectroscopy Can Tell us about Precious Metal Working in Celtic Times, In: I. Ortalli (ed.), Conf. Proc. Ital. Phys. Soc., Vol. 50, Societ Italiana di Fisica, Bologna, 1996, pp. 781784. Gebhard, R., Lehrberger, G., Morteani, G., Raub, C., Wagner, F. E. and Wagner, U., Coin Moulds and Other Ceramic Material: A Key to Celtic Precious Metal Working, In: G. Morteani and J. P. Northover (eds.), Prehistoric Gold in Europe: Mines, Metallurgy and Manufacture, Vol. 280 of NATO ISI Series E: Applied Sciences, Kluwer, Dordrecht, 1995, pp. 273301. Northover, P. and Wagner, U., Private communication. Wagner, U., Wagner, F. E., Husler, W. and Shimada, I., The Use of Mssbauer Spectroscopy in Studies of Archaeological Ceramics, In: D. E. Creagh and D. A. Bradley (eds.), Radiation in Art and Archaeometry, Elsevier, Amsterdam, 2000, pp. 417443. Wagner, U., Gebhard, R., Murad, E., Shimada, I. and Wagner, F. E., The Role of Small Particles in the Study of Archaeological Ceramics, In: J. L. Dorman and D. Fiorani (eds.), Proc. of the Int. Workshop on Studies of Magnetic Properties of Fine Particles and their Relevance to Materials Science, Rome, Italy, Nov. 49, 1991, Elsevier Science Publishers, Rome, 1992, pp. 381392. Gebhard, R., Riederer, J., Schwabe, R., Wagner, U. and Kossack, G., Coloration of Celtic Glass from Manching, In: Y. Maniatis (ed.), Proc. of the 25th Int. Symposium on Archaeometry, Elsevier, Amsterdam, 1989, pp. 207215. Stievano, L., Bertelle, M., Calogero, S. and Wagner, F. E., The Application of 119 Sn Mssbauer Spectroscopy to the Investigation of Glass Coatings: Evolution of the Tin Species in Lead-Rich White Glazes, In: U. Wagner (ed.), Mssbauer Spectroscopy in Archaeology, Hyp. Interact., topical issue, Vol. I, to be published. Friedl, J., Fssel, A., Gebhard, R., Kyek, A., Lehrberger, G., Kobayashi, T., Regen, M. and Wagner, F. E., 197 Au CEMS Study of Celtic Gold Coins, In: I. Ortali (ed.), Conf. Proc. Ital. Phys. Soc., Vol. 50, Societ Italiana di Fisica, Bologna, 1996, pp. 773776. Kyek, A., Wagner, F. E., Lehrberger, G., Pankhurst, Q. A. and Ziegaus, B., Celtic Gold Coins in the Light of Mssbauer Spectroscopy, Electron Microprobe Analysis and X-ray Diffraction, Hyp. Interact. 126 (2000), 235240. Rfer, R., Three Thousand Years of Copper Metallurgy Seen Through the Eyes of Mssbauer Spectroscopy Part III: Copper Losses in Bronze Age Slags, Hyp. Interact. 99(4) (1996), 401407.

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