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Bronze production and tin provenance: New thoughts about the spread of metallurgical knowledge

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AN OFFPRINT FROM
METALS, MINDS AND
MOBILITY
INTEGRATING SCIENTIFIC DATA WITH ARCHAEOLOGICAL THEORY
Edited by
XOSÉ-LOIS ARMADA, MERCEDES MURILLO-BARROSO
and
MIKE CHARLTON
Hardback Edition: ISBN 978-1-78570-905-0
Digital Edition: ISBN 978-1-78570-906-7 (epub)
METALS, MINDS AND MOBILITY
METALS, MINDS AND MOBILITY
INTEGRATING SCIENTIFIC DATA WITH ARCHAEOLOGICAL THEORY
Edited by
XOSÉ-LOIS ARMADA, MERCEDES MURILLO-BARROSO
and
MIKE CHARLTON
Oxford & Philadelphia
Published in the United Kingdom in 2019 by
OXBOW BOOKS
The Old Music Hall, 106–108 Cowley Road, Oxford, OX4 1JE
and in the United States by
OXBOW BOOKS
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© Oxbow Books and the individual authors 2019
Hardback Edition: ISBN 978-1-78570-905-0
Digital Edition: ISBN 978-1-78570-906-7 (epub)
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Front cover: Spearheads from Alcaián deposit (Alcaián lake, Seavia, Coristanco, NW Spain) (Museum of San Antón, A Coruña, Spain)
(photo: ALBIMEH project); base image: Blue Marble: Next Generation, NASA Earth Observatory.
Back cover: A copper chisel from Sultana-Malu Rosu tell settlement (Romania) (photo: T. Ignat).
Contents
Contributors vii
1. Metals, minds and mobility: An introduction 1
Xosé-Lois Armada, Mercedes Murillo-Barroso and Mike Charlton
PART 1: TRANSMISSION OF METALLURGICAL TECHNOLOGIES, KNOWLEDGE AND IDEAS 17
2. On Europe, the Mediterranean and the myth of passive peripheries 19
Tobias L. Kienlin
3. Metal artefacts circulation in the Eneolithic period from southeastern Romania. A case study 37
Catalin Lazar, Adelina Darie, Gheorghe Niculescu and Migdonia Georgescu
4. On Quimbaya goldwork (Colombia), lost wax casting and ritual practice in America and Europe 53
Alicia Perea
5. Bronze production and tin provenance – new thoughts about the spread of metallurgical knowledge 67
Bianka Nessel, Gerhard Brügmann, Daniel Berger, Carolin Frank, Janeta Marahrens
and Ernst Pernicka
PART 2: PRESTIGE ECONOMIES AND EXCHANGE 85
6. Unequal exchange and the articulation of modes of re-production 87
Michael Rowlands
7. Why was (and is) silver sexy? Silver during the 4th–3rd millennia in the Near East and Mesopotamia 97
Susan Sherratt
8. Gold, conspicuous consumption and prestige – a relationship in need of review. The case of
Early and Middle Bronze Age Crete 107
Borja Legarra Herrero
PART 3: CIRCULATION OF METAL AS COMMODITIES 121
9. Biography, prosopography and the density of scienti c data: Some arguments from the metallurgy of
Early Bronze Age Britain and Ireland 123
Peter Bray
10. The role of pre-Norsemen in trade and exchange of commodities in Bronze Age Europe 135
Lene Melheim, Johan Ling, Zo a A. Stos-Gale, Eva Hjärthner-Holdar and Lena Grandin
11. Lead and copper mining in Priorat county (Tarragona, Spain): From cooperative exchange networks
to colonial trade (2600–500 BC) 147
Núria Rafel Fontanals, Ignacio Soriano, Xosé-Lois Armada, Mark A. Hunt Ortiz and
Ignacio Montero-Ruiz
vi Contents
PART 4: CONCLUDING REMARKS 159
12. Mobility, minds and metals: The end of archaeological science? 161
Marcos Martinón-Torres
Index 171
Colour gures 177
XOSÉ-LOIS ARMADA
Institute of Heritage Sciences (Incipit), Spanish National
Research Council (CSIC), Santiago de Compostela, Spain.
DANIEL BERGER
Curt-Engelhorn-Center Archaeometry gGmbH, Mannheim,
Germany.
PETER BRAY
Research Laboratory for Archaeology and the History of
Art, University of Oxford, UK.
GERHARD BRÜGMANN
Curt-Engelhorn-Center Archaeometry gGmbH, Mannheim,
Germany.
MIKE CHARLTON
UCL Institute of Archaeology, London, UK.
ADELINA DARIE
Bucharest Municipality Museum, Bucharest, Romania.
CAROLIN FRANK
Institute of Earth Sciences – Institute of Prehistory,
Protohistory and Near-Eastern Archaeology, Heidelberg
University, Germany.
MIGDONIA GEORGESCU
National History Museum of Romania, Romania.
LENA GRANDIN
Geoarchaeological laboratory, The Archaeologists, The
Swedish History Museums, Sweden.
EVA HJÄRTHNER-HOLDAR
Geoarchaeological laboratory, The Archaeologists, The
Swedish History Museums, Sweden.
MARK A. HUNT ORTIZ
Departamento de Prehistoria y Arqueología, Universidad
de Sevilla, Spain.
TOBIAS L. KIENLIN
Institut für Ur- und Frühgeschichte, Universität zu Köln,
Germany.
CATALIN LAZAR
National History Museum of Romania; University of
Bucharest. ArchaeoScience#RO, Research Institute of the
University of Bucharest (ICUB), University of Bucharest,
Romania.
BORJA LEGARRA HERRERO
UCL Institute of Archaeology, London, UK.
JOHAN LING
Department of Historical Studies, Archaeology, University
of Gothenburg, Sweden.
JANETA MARAHRENS
Curt-Engelhorn-Center Archaeometry gGmbH, Mannheim,
Germany.
MARCOS MARTINÓN-TORRES
Department of Archaeology, University of Cambridge, UK.
LENE MELHEIM
Department of Archaeology, Museum of Cultural History,
University of Oslo, Sweden.
IGNACIO MONTERO-RUIZ
Institute of History (IH), Spanish National Research Council
(CSIC), Madrid, Spain.
MERCEDES MURILLO-BARROSO
Departamento de Prehistoria y Arqueología, Universidad
de Granada, Spain.
BIANCA NESSEL
Institute of Earth Sciences – Institute of Prehistory,
Protohistory and Near-Eastern Archaeology, Heidelberg
University, Germany.
Contributors
viii Contributors
GHEORGHE NICULESCU
National History Museum of Romania, Romania.
ALICIA PEREA
Institute of History (IH), Spanish National Research Council
(CSIC), Madrid (retired); Independent Researcher, Au
Project, Spain.
ERNST PERNICKA
Institute of Earth Sciences – Institute of Prehistory,
Protohistory and Near-Eastern Archaeology, Heidelberg
University; Curt-Engelhorn-Center Archaeometry gGmbH,
Mannheim, Germany.
NÚRIA RAFEL FONTANALS
Departament Història, Universitat de Lleida, Spain.
MICHAEL ROWLANDS
UCL Anthropology, London, UK.
SUSAN SHERRATT
Department of Archaeology, University of Shef eld, UK.
IGNACIO SORIANO
Departament de Prehistòria, Universitat Autònoma de
Barcelona, Spain.
ZOFIA A. STOS -GALE
Department of Historical Studies, Archaeology, University
of Gothenburg, Sweden.
... The sources of the tin in the bronze objects examined may well be in the Erzgebirge region, but it is equally likely that cassiterite ores in Cornwall, the French Massif Central, the Iberian Peninsula and Mt Bukulja were used (see supplementary material Figure S2). However, it is striking that the bronzes of the present sample set show almost the same small tin isotopic variation as determined for EBA bronzes of the Únětice culture from Central Germany with more than 3% tin and dating from the 19th to the 16th centuries BCE (Figure 4a; Brügmann, Berger, Frank, et al., 2017;Nessel et al., 2019). This observation can possibly be explained assuming that the demand for tin was covered by the same deposits over a long period of time (several hundred years). ...
... 3% Sn; Table 2). The isotopic variation in these copper-tin alloys is larger than in the high-tin bronzes (>3% Sn), but the averages of the tin isotope ratios of both types of alloys coincide (Brügmann, Berger, Frank, et al., 2017;Nessel et al., 2019). This shows that the Sky Disc is by no means an exotic object from a metallurgical point of view and that the source of its tin may have to be sought in the same area as that of the other Únětice objects. ...
... 310-311;Nørgaard, 2018). The results from the present study even explain why tin and copper isotopes on early bronze artefacts show no relationship between objects types (Balliana et al., 2012;Mason et al., 2016Mason et al., , 2020Nessel et al., 2019;Powell et al., 2017). If various objects or types of objects were produced in the same workshop from common metal bases, no such dependencies should indeed emerge. ...
Article
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This pilot study addresses the analytical characterisation of 26 well‐known bronze objects of the Early and Middle Bronze Age of Central and Northern Europe. Besides swords and axes of the hoards from Apa, Téglás and Hajdúsámson, the investigation includes the famous Sky Disc and its accompanying finds from the Nebra hoard and several full‐hilted swords from Period I in Denmark. In contrast to former publications, the isotopic systematics of lead, tin and copper are the focus of the present investigation. With a combined approach, we try to relate the either typologically closely linked or otherwise related artefacts with chemical and isotopic proxies by identifying mixing scenarios. The results demonstrate that artefacts from different locations are most likely not directly linked, but mixing lines across isotope systems suggest a production of the items from common sources by mixing of bronze batches (e.g. bronze ingots), which were probably disseminated between 1600 and 1500 BC. This helps to correlate objects of different locations with each other and to draw conclusions upon typological and cultural connections. Isotopic and chemical correlations of objects within the individual hoards on the other hand allow reconstructions of metallurgical practices in single workshops, which for example implies recycling of metal scrap.
... For the sake of completeness, the original tin isotope data (relative to Puratronic) is reported in the electronic supplementary material (Online Resource 3) of this paper, not least to allow comparison with data of our own group formerly using the 124 Sn/ 120 Sn ratio (e.g. Brügmann et al. 2017a;2017b;Nessel et al. 2019;Berger et al. 2019). In addition to the metal samples, the lead isotope composition was also determined for the slag matrix (MA-171261-14 and -15) on the pulverised material with the same MC-ICP-MS at the CEZA. ...
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This paper aims at contributing to a better understanding of the beginnings of tin and bronze metallurgy in Central Asia by investigating a hitherto unique piece of a bronze slag. The object was originally discovered as a stray find only 4 km away from the large copper-tin deposit of Mušiston in Tajikistan. It contains many prills of bronze and copper as well as small charcoal particles. Radiocarbon dating of the charcoal places the slag in a period between 1900 and 1400 BCE and thus in the Late Bronze Age of the region. This date coincides with radiocarbon dates of relics from underground galleries of the Mušiston deposit. Chemical and microscopic examination demonstrated the slag to be a relic of a co-smelting process, in which a natural assemblage of tin and copper minerals was smelted simultaneously. Both the chemical and the tin and copper isotope compositions clearly link the slag to the nearby polymetallic ores from Mušiston, of which an extensive dataset is presented. The artefact’s lead isotope ratios and increased iron concentration in turn indicate intentional fluxing of the original ore charge with iron-dominated ores. These results are the first tangible evidence of a smelting process of tin ores in the entire region and therefore add a new dimension to the findings from previous mining archaeological investigations. At the same time, the results give significant information about the smelting process of secondary polymetallic ores from Mušiston and help in assessing the scientific data of Bronze Age bronze artefacts from Central Asia.
... The first two were most certainly exploited in the Bronze Age. So far, it is not clear when and to what extent the polymetallic deposits in Erzgebirge were mined (Niederschlag et al., 2003), although it is increasingly thought that tin has been extracted there since the Bronze Age (Nessel et al., 2018). This theory has been strongly supported by the evidence of the extraction of tin ore in placer mining at Schellerhau in the Erzgebirge. ...
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A collection of objects associated with prehistoric metallurgy, including casting moulds, a casting core, and a fragment of a tuyere, were found in three metallurgists' graves in the Late Bronze Age cemetery in Legnica, southwest Poland. The finds from these graves presented an opportunity for a scientific investigation of several aspects of Bronze Age metallurgy in this region by applying various analytical procedures to characterise the remains of metals inside the casting moulds. We also analysed metal used for the repair of one of the moulds, and the razor from one of the graves that could have been cast in a mould discovered in another grave. One of the aims of this research project was to establish a possible provenance of the metal used by the population buried in these so-called metallurgists' graves using the chemical and lead isotope analysis. The casting moulds had clear wear marks providing proof of their use. In two cases, the moulds had thick greenish-black layers possibly representing remains of a corroded metal. The chemical compositions of these layers and metal from two other artefacts was investigated using ED XRF and SEM EDS. These analyses showed the diversity of the metals used for castings. Lead isotope analyses using MC ICP MS provided information about the possible origin of lead in the remains from the moulds. The most likely source of this lead is from the ores in the Erzgebirge, in eastern Germany, a few hundred kilometres south west from the site of the graves. The provenance of lead from the razor and from the repair of the mould can be either from the Erzgebirge or Slovak Ore Mountains, or a mixture of these ores.
... Concerning methodology, the provenance of tin has long been investigated by the use of elemental tracers (Tylecote et al. 1989;Rapp et al. 1999) and tin isotope ratios (Gale 1997;Nowell et al. 2002;Haustein et al. 2010;Yamazaki et al. 2014;Brügmann et al. 2017;Nessel et al. 2019). Concerning chemical tracers, several elements (such as W, Bi, In, Mo) have proven potentially interesting to characterize cassiterite ore deposits. ...
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Following animated discussions in the 1990‐2010 period concerning the validity and potential application of Pb isotope data to yield information on ancient metallurgy, recently lead isotope analysis has been extensively applied with alternate success and difficulty to the early stages of copper/lead/silver/tin metal flow in the Central Mediterranean area, arbitrarily defined as including Italy, the Mediterranean Islands, and the surrounding regions for comparison purposes. A wealth of data are now available in the literature, many of them interpreted within local contexts and limited geographical extension, and often within a shifting conceptual modeling frame. A brief review of the recently published data indicate that the metal flow in prehistory and protohistory is far more dynamic than presumed on the basis of the traditionally assumed archaeological models. It is suggested that the isotopic tracers, if correctly applied and interpreted, may substantially help in decoding the metal exploitation and trade patterns at different scales, from the local links between mines and smelting sites, to wider regional or long‐distance trades. The abundant dataset available are however in need of thorough interpretation in terms of wider archaeological and archaeo‐metallurgical questions, possibly by the use of advanced statistical methods and unconventional data mining protocols.
... Tin objects are extremely rare in the archaeological record, and only very few are known from prehistoric contexts (for artefacts in the eastern Mediterranean and the Near East dating from before 1000 BCE see Fig 1; summary of Eurasian finds in [1]). This is probably due to a number of reasons. ...
Article
Full-text available
The origin of the tin used for the production of bronze in the Eurasian Bronze Age is still one of the mysteries in prehistoric archaeology. In the past, numerous studies were carried out on archaeological bronze and tin objects with the aim of determining the sources of tin, but all failed to find suitable fingerprints. In this paper we investigate a set of 27 tin ingots from well-known sites in the eastern Mediterranean Sea (Mochlos, Uluburun, Hishuley Carmel, Kfar Samir south, Haifa) that had been the subject of previous archaeological and archaeometallurgical research. By using a combined approach of tin and lead isotopes together with trace elements it is possible to narrow down the potential sources of tin for the first time. The strongly radiogenic composition of lead in the tin ingots from Israel allows the calculation of a geological model age of the parental tin ores of 291 ± 17 Ma. This theoretical formation age excludes Anatolian, central Asian and Egyptian tin deposits as tin sources since they formed either much earlier or later. On the other hand, European tin deposits of the Variscan orogeny agree well with this time span so that an origin from European deposits is suggested. With the help of the tin isotope composition and the trace elements of the objects it is further possible to exclude many tin resources from the European continent and, considering the current state of knowledge and the available data, to conclude that Cornish tin mines are the most likely suppliers for the 13th–12th centuries tin ingots from Israel. Even though a different provenance seems to be suggested for the tin from Mochlos and Uluburun by the actual data, these findings are of great importance for the archaeological interpretation of the trade routes and the circulation of tin during the Late Bronze Age. They demonstrate that the trade networks between the eastern Mediterranean and some place in the east that are assumed for the first half of the 2nd millennium BCE (as indicated by textual evidence from Kültepe/Kaneš and Mari) did not exist in the same way towards the last quarter of the millennium.
... Accordingly, the bronze manufacturing process itself (ore selection, smelting, alloying and casting processes, recycling practices) is still the subject of many investigations (Radivojević et al., 2018;Rademaker et al., 2018;Radivojević et al., 2013;Laughlin and Todd, 2000;Cuénod T et al., 2015). Tin bronze can be produced in different ways according to the method of supplementation of tin to copper, as tin ore, metallic tin or pre-alloyed tin bronze (Rovira, 2007;Earl, 1994;El Deeb et al., 2015;Nessel et al., 2018): ...
Article
Bronze artifacts from Early Bronze Age in Europe often contain white inclusions in the metallic matrix, that are identified as tin oxides (SnO2 or Cassiterite). These inclusions are interpreted as un-smelted residues coming from the copper ore and are generally mixed with more complex oxidized inclusions, which contain sulfur, antimony, arsenic, silver, nickel and cobalt. The nature, shape and distribution of these partially smelted tin inclusions give information on the alloying process. Depending on the technological context and the geographical areas, the presence of such inclusions might indicate that the material has been produced by selecting and supplementing of raw materials containing SnO2 (e.g. co-smelting). In order to understand the role of tin oxide inclusions in the production of bronzes and possible recycling procedures, a crosscutting investigation has been carried out, based on experimental researches. The results show that tin oxides do not completely reduce after four re melting cycles (recycling) and such a fact is deeply related to the oxygen availability and the dwell time that influences the kinetics of the reaction.
... Accordingly, the bronze manufacturing process itself (ore selection, smelting, alloying and casting processes, recycling practices) is still the subject of many investigations ( Radivojević et al., 2018;Rademaker et al., 2018;Radivojević et al., 2013;Laughlin and Todd, 2000;Cuénod et al., 2015). Tin bronze can be produced in different ways according to the method of supplementation of tin to copper, as tin ore, metallic tin or pre-alloyed tin bronze (Rovira, 2007;Earl, 1994;El Deeb et al., 2015;Nessel et al., 2018): ...
Presentation
Bronze artefacts from Early Bronze Age often contain white inclusions, identified as tin oxides (SnO2). These inclusions are generally mixed with more complex oxidized inclusions containing sulphur, antimony, arsenic, silver, nickel and cobalt, which are interpreted as un-smelted residues coming from the copper ore. The nature, shape and distribution of these partially smelted tin inclusions gives information on the preparation of the alloy from the pure metal. Depending on the technological context and the geographical areas, the presence of such inclusions might indicate that the material has been produced by selecting and supplementing of raw materials containing SnO2 or Cassiterite. With the aim to understand the role of tin oxide inclusions in the production of bronzes and possible recycling procedures, an crosscutting investigation has been carried out, based on both archaeometry and experimental research.
Chapter
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The role that tin from Britain played in the European Bronze Age remains an unanswered question despite nearly two centuries of research. Were the exceptionally rich tin deposits in Cornwall and Devon the main tin source underpinning the massive technological and cultural transition from copper to full tin bronze (bronzization) across Europe and thus enable a pan-continental Bronze Age? Project Ancient Tin is designed to characterise and increase our understanding of Bronze Age tin sources and trade using an interdisciplinary team. An extensive sampling programme of cassiterites and tin artefacts aims to characterise Cornish/Devonian tin sources relative to other potential European sources using three independent techniques: trace element analyses; lead isotope analyses and tin isotope analyses. In addition, extensive Bronze Age archaeological and geological data is being examined and Bronze Age metal trade networks are being reviewed. The project is ongoing, and this paper outlines the main aspects of the research programme.
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The first part by Klaas Veenhof "The Old Assyrian Period" is a critical overview of our knowledge of and at the same time an introduction to the study of the Old Assyrian Period (first two centuries of the 2nd mill. B.C.), as we know it from discoveries in ancient Assur and in particular from the cuneiform archives of the Old Assyrian traders living in an commercial colony (called karum) in the lower town of ancient Kanesh (modern Kültepe) in Central Anatolia. The first chapters establish what "Old Assyrian" is and analyze the chronology and the available sources (material and written). There follows a critical sketch of the publications of and research on the Old Assyrian sources, subdivided in a dozen thematic studies. After a sketch of Old Assyrian history, follows an overview of "the Old Anatolian scene", which deals with the cities, local rulers and the about 40 Old Assyrian commercial settlements in Northern Mesopotamia and Anatolia. A special chapter analyzes the important Old Assyrian commercial treaties. The contribution ends with a detailed presentation of the Anatolian titles and officials and the religious festivals and agricultural seasons that figure as terms of payments in Anatolian debt-notes. The second part by Jesper Eidem "Apum: A Kingdom on the Old Assyrian Route" summarises recent evidence for the history of northern Syria during the period contemporary with the late phase of the Old Assyrian trade. To the detailed study of the sources an Appendix of important texts is added. The book is fully indexed (subjects, texts, geographical names, kings and rulers, gods and temples, persons, Assyrian words) and contains a extensive bibliography.
Article
Increased interest in the fractionation of Sn isotopes has led to the development of several techniques for preparing cassiterite (SnO2, the primary ore of Sn) for isotopic analysis. Two distinct methods have been applied in recent isotopic studies of cassiterite: (1) reduction to tin metal with potassium cyanide (KCN) at high temperature (800 °C), with subsequent dissolution in HCl; (2) reduction to a Sn solution with hydriodic acid (HI) at low temperature (100 °C). This study compares the effectiveness and accuracy of these two methods, and contributes additional methodological details. The KCN method consistently yielded more Sn (> 70% in comparison to < 5%), does not appear to fractionate Sn isotopes at high temperatures over a two hour period, and produced consistent Sn isotope values at flux mass ratios of ≥ 4:1 (flux to mineral) with a minimum reduction time of 40 min. By means of a distillation experiment it was demonstrated that HI could volatilise Sn, explaining the consistently low yields by this method. Furthermore, the distillation generated Sn vapour, which is up to 0.38‰ per mass unit different from the starting material, the largest induced Sn fractionation reported to date. Accordingly, the HI method is not recommended for cassiterite preparation for Sn isotopic analysis. This article is protected by copyright. All rights reserved.