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Tin isotope ratios in early and Middle Bronze Age bronzes from central and southeastern Europe

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UISPP Journal
The Journal of the International Union
for Prehistoric and Protohistoric Sciences
ISSN 261-2782
LATEST RESULTS AND EXAMINATION METHODOLOGIES
OF PRE- AND PROTOHISTORIC METALS AND OTHER
INORGANIC MATERIALS
Guest Editors
BÉLA TÖRÖK, ALESSANDRA GIUMLIA-MAIR, MARIA PIA RICCARDI
PÉTER BARKÓCZY
Editors-in-Chief
Marta Arzarello, François Djindjian, Luiz Oosterbeek
Vol. 2 Issue 1- 2019
UISPP Journal
The Journal of the International Union of Prehistoric and Protohistoric Sciences
Revue de l’Union internationale des sciences préhistoriques et protohistoriques
_____________________________________________________________
EDITOR
Marta Arzarello
Università degli Studi di Ferrara, Dipartimento Studi Umanistici, C.so Ercole I dEste 32 44121 Ferrara (IT)
Editors-in-chief
Marta Arzarello
François Djindjian
Luiz Oosterbeek
Editorial Committee formed by the Chairs of the scientific Commissions of UISPP
Emmanuel Anati
Pablo Arias
Geoff Bailey
Barbara Barich
Éric Boëda
Larbi Boudad
Abdulaye Camara
Stefano Campana
Nicholas John Conard
Eva David
Christophe Falguères
Dominique Grimaud-Hervé
Ya-Mei Hou
Sławomir Kadrow
Marc-Antoine Kaeser
Marie-Hélène Moncel
Marcel Otte
Rebecca Peake
Árpád Ringer
Sandrine Robert
Erika Robrahn Gonzalez
Estela Mansur
Roberto Ontanon-Peredo
Moustapha Sall
Valeriu Sirbu
Natalia Skakun
Iwona Sobkowiak-Tabaka
Apostolos Sarris
Béla Török
Robert Whallon
PUBLISHER
Union Internationale des Sciences Préhistoriques et Protohistoriques
UNIFE C.so Ercole I dEste 32 44121 Ferrara (Italy)
ISSN 2612-2782
UISPP Journal
The Journal of the International Union of Prehistoric and Protohistoric Sciences
Revue de l’Union internationale des sciences préhistoriques et protohistoriques
_____________________________________________________________
Latest Results and Examination Methodologies of Pre- and Protohistoric Metals
and Other Inorganic Materials
Volume 2
February 2019
Issue 2019-1
Editors of the issue
Béla Török
Alessandra Giumlia-Mair
Maria Pia Riccardi
Péter Barkóczy
Editorial Secretariat
Julie Arnaud
Marta Arzarello
FOREWORD
__________________________________________________________________________________
The UISPP Commission on Archaeometry of Pre- and Protohistoric Inorganic Artifacts, Materials and
Technologies organized on the 14th of October 2016, in Miskolc (Hungary) the 1st international
scientific conference of the commission.
The commission provides a platform for scholarly discussion aimed at furthering the dissemination of
new approaches and discoveries, and at promoting best practice in archaeometric research on
metallurgy, glass making, lithic and ceramic technologies in prehistory and protohistory. One of our chief
objectives is opening up access to analytical data, results and conclusions from the broadest possible
range of archaeometric projects and case studies relating to prehistoric and protohistoric artefacts made
from metal, ceramic, glass and stone, with a particular focus on the characterization of raw materials
and on production technologies. By making relevant data accessible to the wider scientific community
and formulating standards for scientific databases, we wish to promote the integration between
archaeometric research and other archaeological approaches. We also strive to formulate standards for
the publication of archaeological scientific data, chemical standards and material structures, and to
create protocols for the archiving and dissemination of existing or “legacy” datasets, which would
otherwise be vulnerable to being lost or overlooked.
Aim of the conference is the presentation of the results of archaeometric case studies and the
examination of methodologies to be employed on Prehistoric and Protohistoric artifacts made of metals
or other inorganic materials. By discussing relevant interdisciplinary research methods and techniques,
we also wish to promote work across academic disciplines and to investigate the relationships and
overlaps between ancient technologies.
Dr. Béla Török, President of the commission
1
TIN ISOTOPE RATIOS IN EARLY
AND MIDDLE BRONZE AGE
BRONZES FROM CENTRAL AND
SOUTHEASTERN EUROPE
ABSTRACT
The paper presents the results of two case studies. A first sample set
includes tin isotopic compositions of 15 bronzes from three large hoards
of the Early Bronze Age Únětice Culture in Central Germany. A major
research question was, whether local tin from the Saxon-Bohemian Ore
Mountains or from different sources was used to produce the artefacts.
The tin isotope composition in the bronzes of these comparably early
hoards of the classical phase of the Únětice Culture shows a small
variation.
The second sample set comprises 16 isotopically investigated objects
from Romania and Hungary, belonging to hoards and settlements. In
addition, the tin isotopic compositions of a dagger and an axe from Crete
were examined. Considering the large geographical distance between the
finds a major research question was, whether the tin isotope composition
of central and southeastern European bronzes differ, and whether the
isotopic compositions of the Aegean bronzes differ from those of the
Carpathian Basin.
Generally, it can be said that the tin isotope composition in this second
sample set show a slightly larger variation than observed in the bronzes
of the Únětice Culture. The Cretan objects show 124/120Sn isotope
compositions, which are higher than the southeastern as well as the
central European samples. This suggests that different tin sources might
have been used to manufacture the bronzes. The paper discusses the
variation of the tin isotope compositions and their bearing on the debate
about tin trade in Europe.
Bianka
NESSEL1,2
Gerhard
BRÜGMANN3
Ernst
PERNICKA1,2,3
1Institute of Earth Sciences,
Heidelberg University,
Im Neuenheimer Feld 234-236
Heidelberg, Germany
bianka.nessel@geow.uni-
heidelberg.de
2Institute of Prehistory, Protohistory
and Near-Eastern Archaeology,
Heidelberg University
ernst.pernicka@geow.uni-
heidelberg.de
3Curt-Engelhorn-Center
Archaeometry gGmbH, Mannheim,
Germany
gerhard.bruegmann@cez-
archaeometrie.de
KEY WORDS:
Tin isotopy
Bronze Age
Únětice Culture
southeastern Europe
bronze objects
UISPP
The Journal of the
International Union for
Prehistoric and
Protohistoric Sciences
Vol. 2 issue 1
February 2019
Tin isotope ratios in bronzes from central and southern Europe
Vol 2-1: 1-11
2
INTRODUCTION
Two decades ago E. Pernicka (1997) summarized the evidence for early usage of bronze in
the eastern Mediterranean and the Near East and came to the conclusion that the first copper-
tin alloys occur in areas without any tin sources. Due to a lack of provenance analyses at that
time, many different origins of tin used to manufacture European bronzes have been
suggested (Dayton 1971; Cleziou and Bertiou, 1982; McGeehan-Liritzis and Taylor 1987;
Durman 1997; Benvenuti et al. 2003; Lo Schiavo 2003; Yener 2008). Suggestions for possible
tin suppliers to Europe were located in no less than three continents. They were partly tied to
known tin mineral sources, oftentimes regardless wether they could be exploited with Bronze
Age technologies or not, and to ancient tin mines (Sos Baynat 1967; Tylecote 1989; Merideth
1998; Boroffka and Parzinger 2003; Cierny et al. 2005; Nezafati et al. 2006; Nezafati et al.
2009; Rodríguez Díaz et al. 2013; Huska et al. 2014; Mason et al. 2016). However, evidence
for Bronze Age mining or metallurgical activities in the vicinity of tin mineralisationes are still
sparse.
Currently the tin deposits of Cornwall and Devon, the Saxon-Bohemian Ore Mountains, and
the Iberian Peninsula seem to be the most likely suppliers to central Europe in the Bronze
Age. The ERC funded project “Bronze Age Tin−Tin Isotopes and the Sources of Bronze Age
Tin in the Old Worldtries to decipher the origin of bronze technology in the 3rd and 2nd
millennium BC by using a multidisciplinary approach. It uses MC-ICP-MS to analyze ore
samples from tin deposits in Eurasia and archeological objects from the Near East and
Europe. Tin minerals (e.g. cassiterite) from different tin provinces are investigated to obtain
an insight of their tin isotopic systematics in order to check, if these deposits can be
differentiated. This is, of course, a prerequisite for any provenance discussion. A broad
comparison of the results will produce a deeper understanding of the inter- and intra-regional
raw material distribution and technological transfer. Major project aims are to expand the
number of tin isotope compositions and to investigate the spread of bronze metallurgy as an
important innovation through Europe and the Near East. Archaeological context information
and the results of tin isotopy will be combined in order to achieve this.
RESEARCH HISTORY
Early studies of the isotopic compositions in archaeological bronze artefacts, bronzes made
of tin bearing raw copper and cassiterite showed that the isotopic fractionation in samples of
all materials is very small (Rosman et al. 1984; McNaughton and Rosman 1991; Budd et al.
1994; Yi et al. 1995; Gale 1997; Begemann 1999). The analytical advances provided by the
much more precise MC-ICP-MS measurements enabled new archaeological provenance
studies of tin minerals and copper-tin alloys. The multicollector observes very small tin isotope
variations up to 0.55 per unit mass (Lee and Halliday 1995; Clayton et al. 2002; Haustein
et al. 2010; Balliana et al. 2013; Yamazaki et al. 2013).
Haustein et al. (2010; 2014); published about 80 tin isotope analyses of cassiterite from
different deposits in southern England and the Saxon-Bohemian Ore Mountains using the
δ122/116Sn and δ117/119Sn. Cassiterite from both tin provinces shows a large variation in
the values of this ratio and a substantial overlap of the data of both sources. They also pointed
out that, despite the overlap of values, the ores of the Saxon-Bohemian Ore Mountains tend
to have lighter tin isotopic compositions (δ122/116Sn = 0.34±0.36 ‰) than those of southern
England (δ122/116Sn = 0.48±0.51 ‰). Furthermore, they showed, that there is no difference
between cassiterite from primary or secondary ores (Haustein 2014).
Tin isotope ratios in bronzes from central and southern Europe
Vol 2-1: 1-11
3
PREMISES AND METHODS
Cassiterite was probably the major mineral used for tin processing in the Bronze Age. It can
be collected in alluvial environments like rivers and might be discovered during gold washing
activities in similar settings. Stannite is the major sulfidic tin mineral but occurs rarely. In
addition, stannite is mainly found in primary ore veins, which makes it hard or impossible to
mine.
It needs to be emphasized, that tin minerals collected from alluvial deposits of different local
sources could have been mixed by ancient metallurgists. Therefore, a preliminary but
necessary premise for a successful provenance analysis is that the cassiterite used to
manufacture a particular batch of bronzes is derived from a single source. Similar
considerations apply for a possible re-melting of bronzes, which would have a homogenization
effect. The chemical and isotopic signatures would be averaged leading to a fairly small range
of values. But, as it will be pointed out later, the tin isotopic analyses results show a broad
variation, which is a strong argument against re-melted objects in the presented sample sets.
A new analytical method needed to be established to guaranty a very high measurement
precision. The tin needs to be liberated from the mineral matrix, which is achieved in the Curt-
Engelhorn-Zentrum für Archäometrie in Mannheim. Cassiterite is difficult to dissolve with
mineral acids, therefore it is reduced with potassium-cyanide and thereby transformed into
dissolvable tin. After many experiments this can be considered as the best working procedure
(unpublished data). Brügmann et al. (2017) recently published a comprehensive description
of the analytical method.
DISCUSSION
In the following, the tin isotopic compositions of Early and Middle Bronze Age bronze artefacts
from two different European regions will be presented and discussed. Bronzes of the central
European Únětice Culture will be compared with contemporary and slightly younger metal
objects from various regions and cultural environments in southeastern Europe. The major
aim was to determine whether the isotopic composition of the bronzes is similar or differs.
Following this, a possible identification of the tin provenance will be evaluated.
Sample set I – bronzes of the Únětice Culture
The first sample set contains bronzes from the Saxo-Thuringian subgroup of the central
German Únětice Culture (2300 and 1500 BC). The archaeological Culture is distributed over
a fairly large area in eastern and central Germany, including the Harz Mountains and the
western part of the Saxon-Bohemian Ore Mountains (Zich 2010). Therefore, its distribution
area comprises potential tin ore sources.
Nevertheless, previous studies suggested that the tin of the Nebra Sky Disc, dating to the very
end of the Únětice Culture around 1600 BC (Meller 2010), is most likely derived from the tin
province in Cornwall and Devon rather than from the much closer Saxon-Bohemian ore
mountains. Therefore, it seemed appropriate to choose older bronzes from the Únětice
Culture from the vicinity of the Nebra hoard for further tin isotopic analyses. A major research
question was whether at the beginning of the Únětice Culture local tin ore from the Saxon-
Bohemian Ore Mountains was exploited, and a change of raw material sources through 700
years of tin use in the area can be observed.
The samples were taken from bronzes of three large hoards in the area of Saxon-Anhalt,
namely Dieskau II (1950-1750 BC) (Rassmann 2004) and III (2200-1950 BC) (Freudenreich
Tin isotope ratios in bronzes from central and southern Europe
Vol 2-1: 1-11
4
and Filipp 2014) as well as Gröbers-Bennewitz (2000-1800 BC) (Rassmann 2010). The latter
contains 293 flanged axes, seven of which were analysed. The other two finds contain
bronzes with different functions, such as tools, jewelry and weapons. From the Dieskau II
hoard a flanged axe, two bracelets and a dagger were analysed, while from the Dieskau III
hoard a double axe, two rings and eight flanged axes were chosen for isotope analysis. As
previous studies showed, the objects from Bennewitz were produced from chalcopyrite. This
also applies to a couple of objects from the Dieskau II hoard (Nessel et al. 2015). The tin
content is highly variable in the Dieskau-bronzes (<0.1 to 11 wt.%), whereas the artefacts of
Gröbers-Bennewitz show a rather limited range from 1.9 wt.% to 6.1 wt.%. More than 3 wt.%
tin is not expected in fahlore or chalcopyrite ores, which suggests an intentional alloying of
copper and tin during or after the smelting process.
___________________________________________
Fig. 1: Tin isotopic composition of bronzes from the Gröbers-
Bennewitz and Dieskau hoards compared to southeastern
European finds.
___________________________________________
Fig. 2: Comparison of the tin isotopic composition of bronzes from
the Únětice Culture with those of ore deposits from the Saxon-
Bohemian Ore Mountains and Cornwall/Devon.
Fig. 1 shows the tin isotopic composition of bronzes from all three hoards. Although different
copper ore sources are suggested by the chemical composition of the finds (Junghans et al.
1968; unpublished data), the tin appears to derive either from one source with a very
heterogeneous isotopic composition or from different ore sources of similar composition. The
average of δ124/120Sn for the Gröbers-Bennewitz bronzes is almost indistinguishable from
those of the Dieskau artefacts (Nessel et al. 2015).
New and more precise data of ores from the tin provinces in the Saxon-Bohemian Ore
Mountains and southern England demonstrate that the tin isotope ratios show a larger
variation than observed in previous studies (Brügmann et al. 2016). A comparison of the tin
isotopic composition of tin deposits in the Saxon-Bohemian Ore Mountains and southern
England with those of the Únětice bronzes shows that the data have a large overlap (Fig. 2).
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0 5 10
δ124/120Sn
Sn wt.%
Southeastern European bronzes
Únětice bronzes
-1,0
-0,8
-0,6
-0,4
-0,2
0,0
0,2
0,4
0,6
- 1 , 5 - 1 , 0 - 0 , 5 0 , 0 0 , 5 1 , 0
δ124/120Sn
δ122/116Sn
Gröbers Bennewitz
Dieskau II
Dieskau III
Saxony-Bohemian Ore Mountains
Cornwall
Tin isotope ratios in bronzes from central and southern Europe
Vol 2-1: 1-11
5
Therefore, it is currently difficult to decide, from which of the two provinces the tin in the
sampled bronzes actually derived.
Sample set II – Southeastern European bronzes
A second sample set comprises Early and Middle Bronze Age bronzes from southeastern
Europe. In contrast to Central Europe the archaeological situation in this region is more
complex. Therefore, the sample set contains bronzes, which are geographically much wider
distributed and date from around 2000 BC to 1600 BC.
In southeastern Europe there is no single dominating archaeological Culture in this period that
can be exclusively linked to an early use of copper-tin alloys. This can only be observed at
the very end of the early phase of the Bronze Age (ca. 2500-2000 BC; Motzoi-Chichideanu
2012; Kiss et al. 2015; Fischl 2015) as the term is currently used in the regional chronological
systems. A wider distribution of bronzes can be observed from the regional Middle Bronze
Age (2000-1450; BC Motzoi-Chichideanu 2012; Kiss et al. 2015; Fischl 2015) onwards.
In the first half of the 2nd millennium, the west of Transylvania is characterized by several
archaeological cultural groups. Besides the Hatvan-Culture (2200-1800 BC), which covers
northeast Hungary as well as the Tisza region and northeastern Transdanubia, the slightly
younger Vatya-Culture (1950-1650 BC;), which is located in northeast Transdanubia as well
as in the plain between Tisza and Danube, are major cultural complexes and can be divided
in several sub groups. Since archaeological cultures in the area are exclusively defined by the
typologically and stylistically different appearance of pottery, metal objects cannot be
assigned to them. Nevertheless, the Hajdúsamson hoard (Zoltai 1908; Mozsolics 1967; Dani
2013), from which a sword was sampled, is located in the area of the Gyulavarsánd Culture
(Otomani Culture in Romanian Terminology; Meier-Arend 1992). The sampled bronzes from
Transsylvania were mainly found in the area of the Wietenberg Culture (ca. 1800-1400 BC;
Boroffka 1994; Dietrich 2014), while those of southern Romania came to light in the area of
the early phases of the Tei Culture (Leachu 1966) and the Verbicioara-group (Berciu 1961;
Nica 1998).
The sample set comprises of 15 axes, three Ösenrings, three swords and one pin from five
hoards and two settlements in Romania. The oldest bronzes are five shafthole axes from the
hoards of Sinaia and Borleşti (Vulpe 1970), which mark the transition from the Early to the
Middle Bronze Age according to the southeastern European terminology. The Ösenrings
come from the early Middle Bronze Age mixed hoards of Maglavit (Soroceanu 2012) and
Predeal (Târlea et al. 2009). Included in the sample set are also a pin with a triangular head,
found in layer II of the Truşeşti (Movila Şesul Jijiei) settlement (Petrescu-Dîmbovita 1954),
and a flanged axe, which might belong to a small hoard of two axes, found within a settlement
in Braşov (Junghans et al. 1968; Soroceanu 2012). Stylistically and technologically more
advanced slightly younger shafthole axes of different types (Háyek 1947/48; Vulpe 1970;
Neugebauer-Maresch 2000) and two of the earliest swords in Europe from the Apa hoard
(Popscu 1937-40; Soroceanu 2012; Pernicka et al. 2016) were also analysed.
A riveted, triangular dagger from store-room δ of Tholos A in Plátanos (Xanthoudídes 1924;
Legarra-Herrero 2011) and an axe from the oval house in Hamáizi (Chamezi) on Crete were
also chosen for the sample set (Schmidte 1992) in order to compare the isotopic compositions
of bronzes from different southeastern European regions. The Tholos is dated to the end of
the Early Minoan and early Middle Minoan phase of the Aegean Bronze Age (EM III: 2600-
1900 to MM I: 1900-1600 BC), while the oval house is dated more roughly from the Early
Minoan to the Middle Minoan I period (1600 BC).
Tin isotope ratios in bronzes from central and southern Europe
Vol 2-1: 1-11
6
Chemically the bronzes are similar to the Únětice bronzes of the Gröbers-Bennewitz hoard,
because their copper component has low Sb, As and Ag contents, which is typical for
chalcopyrite assemblages (Fig. 3). The tin distribution among the finds differs less compared
to the previous sample set. The differences in the δ124/120Sn relation of bronzes with higher
tin contents are similar to the bronzes from Central Germany. The values of the latter range
from 0.17 to 0.29 ‰, while the values of the southeastern European sample set vary from 0.1
to 0.4 (Fig. 1).
The variation of the tin isotope ratios in the southeastern European bronzes is slightly greater
than those of the Únětice culture. Nevertheless, they still plot within the range of the Cornwall
and Devon Cassiterite as well as those of the Saxon-Bohemian Ore Mountains. At least for
the Romanian and Hungarian artefacts both sources can be considered as potential tin
supplier, and a preference for a certain origin of the raw material used to alloy the bronzes
can currently not be determined.
The composition of bronzes from Crete differs from those of Romanian and Hungarian
bronzes. The tin isotopic values of an axe from Crete are located at the very edge of the
average distribution of the combined sample sets and the values of a dagger are plotted even
further afield from the average value range (Fig. 4).
___________________________________________
Fig. 3: Tin isotopic composition of bronzes from south-
eastern European finds compared to those of Únětice
bronzes.
This suggests that the tin in the Minoan bronzes probably came from a different source than
the bronzes of the Carpathian Basin. Although the ratios do not match the average values of
the southern English ore samples or those from the Saxon-Bohemian Ore Mountains, it is
currently not possible to determine where this tin came from.
CONCLUSION
The tin isotopic ratios of cassiterite from southern England and the Saxon-Bohemian Ore
Mountains vary greatly. A determination of tin isotope ratios in Únětice bronzes from the end
of the 3rd and the beginning of the 2nd millennium BC show isotopic compositions similar to
those of both possible sources. Exploitation of one or both tin provinces to manufacture these
bronzes is therefore highly likely.
Tin isotope ratios in bronzes from central and southern Europe
Vol 2-1: 1-11
7
A derivation of the used tin from only one single ore source is possible, but since the overlap
of the tin isotopic compositions is so large, the exact provenance of the tin used in early central
European bronzes cannot be determined yet. However, the tin used to manufacture the Sky
Disk of Nebra, derived more probably from Cornwall and Devon than from the Saxon-
Bohemian Ore Mountains because its tin isotope composition differs significantly from other
analysed Únětice objects (Balliana et al. 2013). The disk was probably manufactured and
used between 1750 and 1650 BC before it was deposited around 1600-1550 BC (Meller
2010). This suggests the exploitation of more than one ore source from the beginning of the
Early Bronze Age onwards, and at least a temporary established tin exchange between the
British Isles and central Europe (O’Connor 2010). Cornish tin was utilized for producing the
Sky Disk, whereas other source(s) were used to produce bronzes for everyday use.
___________________________________________
Fig. 4: Comparison of the tin isotopic composition of
Cu-alloys from southern European finds with those of
ore deposits from the Saxon-Bohemia Ore Mountains
and Cornwall/Devon.
Southeastern European bronzes from the first half of the 2nd millennium BC, show only
slightly larger variations of the tin isotope ratios than the Únětice bronzes. A western origin of
the tin used to produce them is currently most likely, particularly because their tin isotopic
compositions plot within the common range built up by cassiterite samples from the Saxon-
Bohemian Ore Mountains and Southern England. As a result, it is currently not possible to
determine the provenance of the alloyed tin in most of the analysed bronzes.
There existed a trade network between the two regions, which is indicated by a number of
central European bronze types found in various contexts in southeastern Europe, such as the
Mokrin cemetery (Girić 1971; O’Shea 1996; Bösel 2008; Wagner 2009). There almost all
bronzes with high tin contents are of central European types, typical of the Únětice Culture.
Given a comparably later widespread distribution of tin bronzes in the Carpathian Basin
between 1800 and 1700 BC, metal trade between southeastern Europe and the Únětice
Culture is highly likely.
However, the two objects from Crete show tin isotopic compositions, which are not only
heavier than those of the southern European and the Únětice Culture sample set, but they
also plot outside the average range defined by cassiterite from Southern England and the
Saxon-Bohemian Ore Mountains. This suggests that these bronzes were manufactured with
tin ore from a different source. Currently it is not possible to determine the provenance of the
-1,0
-0,8
-0,6
-0,4
-0,2
0,0
0,2
0,4
0,6
-1,5 -1,0 -0,5 0,0 0,5 1,0
δ 124/120Sn
δ 122/116Sn
southeastern European bronzes
Cretan bronzes
Saxon-Bohemian Ore Mountains
Cornwall
Tin isotope ratios in bronzes from central and southern Europe
Vol 2-1: 1-11
8
tin used in the Aegean region in the 2nd millennium. BC. Further analyses and comparisons
of isotopic compositions of tin ores and bronzes might produce a better understanding of raw
material distribution systems in Bronze Age Europe.
ACKNOWLEDGMENTS
This research was funded by the Advanced Grant no. 323861 of the European Research
Council for Ernst Pernicka. We are grateful to the reviewers and the publishing house for their
helpful suggestions regarding this paper.
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... Large ranges of Sn isotope composition of ore samples within individual deposits/camps result in substantial overlaps between ore-bearing localities. For example, several studies have documented the extensive overlap between the isotopic signatures of the ores of Cornwall and Erzgebirge (Haustein et al., 2010;Berger et al., 2019;Nessel et al., 2019), leading some researchers to conclude that Sn isotopes cannot be used to distinguish between these two major regions reliably (e.g., Nessel et al., 2019). In addition, experimental studies suggest that significant fractionation may be induced during the smelting process, which could impart a mismatch between an artifact and its source ore (Berger et al., 2018). ...
... Large ranges of Sn isotope composition of ore samples within individual deposits/camps result in substantial overlaps between ore-bearing localities. For example, several studies have documented the extensive overlap between the isotopic signatures of the ores of Cornwall and Erzgebirge (Haustein et al., 2010;Berger et al., 2019;Nessel et al., 2019), leading some researchers to conclude that Sn isotopes cannot be used to distinguish between these two major regions reliably (e.g., Nessel et al., 2019). In addition, experimental studies suggest that significant fractionation may be induced during the smelting process, which could impart a mismatch between an artifact and its source ore (Berger et al., 2018). ...
... Placer mining at Altenberg is suggested to have been active by the early 2nd millennium BC based on 14 C dates from charcoal found in association with an extraction site in weathered mineralized granite, over which ridges of gravel were piled (Tolksdorf et al., 2019). In addition, Nessel et al. (2019), found that Early Bronze Age Únětice artifacts have similar isotopic ratios to cassiterite ores from Erzgebirge, despite being from different hoards and having variable tin contents. Accordingly, the authors concluded that local ore sources were exploited to produce this early bronze. ...
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We report the largest published dataset to date of Sn-isotopic compositions of Bronze Age artifacts (338) along with 150 cassiterite samples (75 new) from six potential tin ore sources from which the tin in these artifacts were thought to have likely originated. The artifacts are from a broad area, Central Europe through the Central Balkans, and the six tin sources are Cornwall, three sites in the Erzgebirge, and two sites in Serbia. A clustering analysis on mean site-level isotopic values of δ¹²⁴Sn identifies regional variation that can be attributed to the use of different tin ore sources in different regions. Therefore, geographically meaningful regions were identified to group the Bronze Age artifact assemblages and a probabilistic, Bayesian analysis was performed to determine the proportional contribution of each tin source to each regional assemblage. Artifacts enriched in heavy isotopes (δ¹²⁴Sn > 0.7‰) that cluster in west-central Serbia are likely associated with the ores from Mt. Cer in west Serbia. Mixed artifact assemblages (high and low δ¹²⁴Sn) in this region are attributed to the use of cassiterite from the two Serbian sites (Mt. Cer and Mt. Bukulja). Moderate composition artifacts that occur north of the Middle Danube in Vojvodina, Transylvania, and Central Europe are likely associated primarily with ores from the West Pluton of the Erzgebirge. Compositionally light bronzes (δ¹²⁴Sn < 0.2‰) in southern Serbia and the lower Danube river valley cannot be linked to a documented ore source. There is no indication of the use of ores from Cornwall or the East Pluton of the Erzgebirge in Central Europe and the Balkans during the Late Bronze Age.
... Most recently, new methods associated with nontraditional isotopic systems, including copper, silver, and tin, have been applied to provenance studies o metal artiacts with varying degrees o success. O these, tin isotopes have received the greatest interest, as the only available means o ngerprinting tin in alloys such as bronze (Balliana et al., 2013;Berger et al., 2018Berger et al., , 2019Berger et al., , 2021Berger et al., , 2022aBower et al., 2019;Brügmann et al., 2017a;Haustein et al., 2010;Mason et al., 2016;Mason et al., 2020;Nessel et al., 2019;Powell et al., 2022;Yamazaki et al., 2014). ...
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... Discerning particular classes of material based on unique characteristics such as lead content extends this potential to the level of basic process reconstruction, opening the way for hypotheses on hyper-local material use. Trace metal profiles and tin isotopes have been applied to tin provenance studies (Begemann et al., 1999;Haustein et al., 2010;Berger et al., 2019;Bower et al., 2019;Mason et al., 2020); however, compositional variations within deposits result in significant overlaps between tin ores across Europe and Asia (Nessel et al., 2019;Berger et al., 2019;Mason et al., 2020). Therefore, additional independent variables are required to deduce tin sourcing and distribution patterns (Stephens et al., 2021). ...
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15 16 Recent analytical developments in the field of mass spectrometry have made possible accurate 17 measurements of "non-traditional" isotopic ratios of elements such as Fe, Cu, Ag, Sn, Sb and Hg. 18 The stable isotopes of these elements do not have any radioactive parents, but their ratios undergo 19 limited fractionation from various causes, most of them mass-dependent. These effects can lead to 20 variation in isotopic ratios of natural materials (minerals, rocks, ores, etc.) and in archaeological 21 artifacts derived from them. Research since 2010 has investigated whether variation in these 22 isotopic ratios can be used to infer the geological provenance of archaeological materials, 23 including bronze and glass. Here we review recent research on these isotopic systems in 24 archaeology, their principal applications, as well as expected future developments in their use. We 25 conclude that none of these isotopic systems are likely to be very useful for provenance, mostly 26 because of limited ranges of isotopic ratios and/or extensive overlap between the isotopic ratios of 27 most geological sources. Copper isotope ratios are however a reliable method for inferring the type 28 of ore (supergene versus hypogene) smelted to produce copper, and recent studies indicate that 29 silver isotope ratios can also be applied to this effect. 30 31
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Altogether 29 Early and Middle Bronze Age metal objects from Romania including six from the famous Apa hoard were analysed for their chemical compositions and lead isotope ratios. In order to determine the provenance of the copper, these geochemical signatures were compared with copper ores from geological deposits in central and southeastern Europe, which had been exploited in the Bronze Age. It can be concluded that the copper of the implements from the Apa hoard most likely derives from the east Alpine Mitterberg region while the other Middle and Late Bronze Age objects from Romania largely consist of Slovakian copper.
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Ireland is important in the early metallurgy of northwest Europe, for it has given us a large majority of the Early Bronze Age artefacts from the whole British Isles. Is there tinore to have been mined in early Ireland to produce this bronze or must it have come from elsewhere?
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An analytical technique is presented for isotope analysis of a Sn ore mineral, cassiterite. Hydroiodic acid was used to successfully decompose the cassiterite samples. An extraction chromatographic material, TRU resin was utilized for the chemical purification of Sn. Although it has been confirmed that this purification process causes isotopic fractionation, the effect can be corrected. The purification method was used to investigate natural isotopic variations in Sn in cassiterite from Asian countries (Japan, China, Thailand, and Malaysia), via multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Consequently, isotopic variations as large as 0.77%o in (124)sn/Sn-120 were observed for cassiterite samples from Japan and China. The isotopic fractionations of all the samples were dependent on isotope mass. However, the cause of Sn isotopic variation is yet to be established.
Article
Tin is a rare metal that is essential for making bronze, the defining technology of the Bronze Age. The source(s) of tin for Aegean bronze is undetermined but several small Bronze Age tin mines have been documented in the circum-Aegean region. The discovery of Bronze Age archaeological sites in West Serbia near a tin placer deposit on the flanks of Mt. Cer led to an investigation of this site as a potential additional Bronze Age tin mine in the region. Geochemical prospecting of stream sediments flowing from Mt. Cer allowed for categorization of streams based on relative tin grade. Tin grade is highest in the Milinska River, a likely combination of a broad catchment area with multiple ore-bearing tributaries, and a topographic profile that favors accumulation placer deposits. Pedestrian survey of cornfields along the southern pluton margin discovered archaeological sites spanning the Neolithic to the Iron Age. Unlike older and younger sites, those of the Bronze Age were found only along the Milinska and Cernica Rivers where placer tin grades are highest, but appear to be absent where tin is scarce or absent. This suggests that these sites were situated to exploit the tin ore.