Lead Isotope Analysis Research Articles

Dutch or Iranian? Technical study of a seventeenth-century painting on paper from Gesina Ter Bosch\u2019s scrapbook

A scrapbook compiled between 1660 and 1687 by Gesina ter Borch (1631–1690), a female artist from the small town of Zwolle in the Netherlands, contains an intriguing painting on paper of a full-length portrait of a young Iranian. Although the figure wears the attributes in vogue at the Safavid court of Isfahan, certain elements seem rather incongruous and peculiar. The general composition appears static and rigid, an impression reinforced by an unusual black painted background. Stylistic differences within the painting were also observed, hinting at alterations to the original painting. To investigate the history of the painting and to reconstruct the original composition and identify the later additions, perhaps made by Gesina herself, the painting was examined with different imaging and analytic techniques available at the Conservation and Science Department of the Rijksmuseum. This allowed the research team to discriminate between pigments used for the original composition and pigments used to conceal damaged areas of the painting and added pictorial elements. After interpreting scientific results, as well as historical findings, it was possible to shed light on the use of specific pigments, namely lead white and smalt, and on the possible misinterpretation of some details, such as the cup held by the young man. The results of macro X-ray fluorescence scanning (MA-XRF) and lead isotope analysis, viewed in the light of information about the economic and cultural exchanges between Iran and the Netherlands in the seventeenth century, fed new theories about the origin and history of this painting. The painting, originally made in Iran in the style of Riza Abbasi, the head of the Emperor Shah Abbas’ library, ended up in Gesina ter Borch's workshop and may have been ‘restored’ by the artist to improve its condition and to match her tastes.

Late Mesozoic post-orogenic granitoids and its metallogenic implications: Constraints from Nantai porphyry Mo deposit, Northern Qinling, China

Late Mesozoic Nantai porphyry Mo deposit is located in the Northern Qinling terrane, eastern China. The intrusions at Nantai include lamprophyre, quartz porphyry, and granite porphyry. Among them, molybdenum mineralization is associated with quartz porphyry and granite porphyry. The ore-bearing porphyries and ore-barren lamprophyres emplaced at ca. 155–146 Ma and ca. 156–146 Ma, respectively. The calculated zircon ΔFMQ values for Nantai felsic and mafic intrusions are –5.0 to +9.1 (an average of + 2.2) and –6.7 to +5.0 (an average of +1.2), which are similar to those of contemporaneous giant Mo deposits in the south margin of the North China Block. The quartz porphyry and granite porphyry are characterized by relatively high SiO2 (73.39–75.49%), K2O (4.24–9.61%), and Rb (291–552 ppm) contents, but low total Fe2O3 (0.13–0.83 wt%), MgO (0.1–0.3 wt%), P2O5 (0.01–0.04 wt%), Sr (22.4–141.0 ppm) and Ba (79.8–1757 ppm) concentrations. These granitic samples have TDMC ages of 2204–1592 Ma, corresponding to negative εHf(t) values of –15.8 to –6.2. Geochemical and zircon Lu-Hf signatures as well as lead isotopic analyses for Nantai granitoids suggest that they belong to the high-fractionated I-type granites and were derived from partial melting of lower continental crust with coeval mantle-derived magma contribution. The lamprophyres show low SiO2 (47.59–49.08%) and Rb (96–120 ppm) contents, whereas they have high Ba (1598–2236 ppm), and Sr (771–990 ppm) concentrations, as well as a lack of negative Eu anomalies. The concentrated εHf(t) values (–0.6 to + 3.3), high (Hf/Sm)PMN and La/Sm ratios, as well as Pb isotopic features, indicate that they were derived from an enriched lithospheric mantle that had been metasomatized by subducted components with some crustal material contribution. Combined with our datasets and previous studies, we suggest that the Nantai porphyry Mo deposit formed in a post-orogenic setting.

Roman lead ingots from Macedonia\u2014the Augustan shipwreck of Comacchio (prov. Ferrara, Italy) and the reinterpretation of its lead ingots\u2019 provenance deduced from lead isotope analysis

A shipwreck of the 3rd/2nd decade BC found near Comacchio (prov. Ferrara, Italy) in 1980 contained not only well-preserved technical equipment and commercial goods but also 102 Roman lead ingots. Since then, the origin of the ingots has been intensively discussed. Domergue et al. (2012) connected the epigraphic elements with lead isotope analyses and favored the southeastern Spanish lead ore mines being the source of the lead metal. An origin from the Balkan region (Illyricum) was favored by Dušanić (2008). Due to our investigations, both assumptions cannot be maintained. We present a new interpretation of the lead’s isotope signature which best match data of ore deposits from Chalkidiki, Thasos island, and Pangaion mountains in the northern Aegean region.

Lead isotope analysis of tin bronze objects from the Iron Age site at Baba Jilan, Luristan, western Iran

Lead isotope analysis of tin bronze objects from the Iron Age site at Baba Jilan, Luristan, western Iran

A provenience study of Bronze Age metal objects from the Hami Basin, Xinjiang, China

Lead isotopic analysis on metals of the Bronze Age of Hami Basin (1800-400 BCE) principally focus on the early sites such as the Tianshanbeilu cemetery and Liushugou Site. Opinions on their provenience are wildly divergent. This research presents 29 lead isotope data of metals from Wupu cemetery (1000-400 cal BCE) as an important site from the late period and ten from Tianshanbeilu cemetery as well as their chemical composition and metallographic structure. Combined with existing data, this article comprehensively discusses the possibly existing circulation network of metal resources between the Hami Basin and the other three areas, namely the southern Altai Mountains, the Hexi Corridor, and the West Tianshan Mountains during the Bronze Age, and provides a new understanding of the role played by the Hami Basin in the Bronze Age as one of the cultural passageways linking the eastern Eurasian steppe and the Hexi Corridor.

A contribution to the technology and sources of lead in Byzantium: lead isotope analysis of ten Byzantine seals

Abstract This article presents the results of lead isotope analysis of ten Byzantine seals from the sigillographic collection of Robert Feind (Cologne). The report is preceded by an overview of pre-existing studies on lead use in the Byzantine Empire and a presentation of the investigated seals datable to the Early Byzantine (4 specimens), Middle Byzantine (5 specimens) and Late Byzantine period (1 specimen). Three seals are of imperial issue. The results of the analysis of lead are compared against the results of isotope analysis of other silver and lead artefacts from Late Antiquity and the Late Byzantine period. The isotop analysis leads to the following conclusions: (a) Many of the seals have isotope ratios consistent with Aegean-Bulgaria-Western Turkey sources; (b) Reused lead was also employed in the manufacture of seals; (c) There appear to be significant chronological and regional differences in the lead used for casting blanks in the eastern Mediterranean. The number of lead seals subjected here to analysis is admittedly too small for the results to be fully representative; still, they provide a starting point for more similar studies which will preferably include excavation finds with known and secure provenance.

Provenance of Zhou Dynasty bronze vessels unearthed from Zongyang County, Anhui Province, China: determined by lead isotopes and trace elements

Thirteen Zhou Dynasty bronze vessels and two slags from Zongyang County along the north bank of the Yangtze River in Anhui were analyzed by LA-MC-ICP-MS and EDXRF. The results of lead isotope analysis showed that there were two kinds of lead materials in the Zongyang bronzes. Vessels in Class I, thought to have originated from the Wannan region were primarily used during the Western Zhou and the following Spring and Autumn period; while those in Class II, possibly from the local mines in Zongyang County, were mainly present during the Warring States period. Such a shift in the ore material sources is also revealed by the trace element analysis of the Zongyang bronzes. With reference to the relevant historical documents, we suggest that the transformation of the bronze material sources might have been associated with the changes of the political situation during the Zhou Dynasty.

From peaks to ports: Insights into tin provenance, production, and distribution from adapted applications of lead isotopic analysis of the Uluburun tin ingots

Lead isotope analysis (LIA) can be applied to tin provenance studies when both the U–Th–Pb characteristics of cassiterite and potential Pb contamination are taken into account. As cassiterite (SnO2) contains higher concentrations of U than Pb and negligible Th, radioactive decay increases 206Pb/204Pb and 207Pb/204Pb ratios in cassiterite over time. However, 208Pb/204Pb ratio retains its primary value and can be correlated with LIA databases. A majority of documented Bronze Age tin ingots from Europe have Pb in excess of the 5 ppm maximum that can be derived from Cenozoic to Late Paleozoic cassiterite. A minute mass of galena (PbS) in the ore concentrate is sufficient to mask the cassiterite-derived lead, as would the addition of any lead contaminant introduced in the smelting/casting process. If the galena is cogenetic with the cassiterite, then LIA will be unaffected. The inclusion of uranium-rich minerals in the tin ore concentrate is another potential source of excess lead. In this case, the additional Pb is uranogenic, and so 206Pb/204Pb and 207Pb/204Pb will reflect the age of the uranium minerals, but 208Pb/204Pb will retain its primary value. If the U-minerals are cogenetic or coeval with tin mineralization, then a Pb isochron age will indicate the age of the ore.Between 1984 and 1994, at least 117 ingots, or roughly one tonne, of tin was raised from the Late Bronze Age Uluburun shipwreck (ca. 1320 B.C.). Over half of the analyzed ingots from this wreck site have high Pb concentrations (>100 ppm), indicative of contamination from non-radiogenic lead associated with lead metal or galena. LIA indicates that the Pb originated from the Pb–Ag-rich Bolkardağ region of the south-central Taurus Mountains. A second group of approximately 28 tin ingots with lower Pb content (<100 ppm) contain additional uranogenic Pb but retain 208Pb/204Pb compositions that overlap with the ca. 300 Ma tin regions of Western Europe and Central Asia, with the most likely source being the Tienshan Mountains in Kyrgyzstan, Tajikistan, and Uzbekistan.By compensating for previous uncertainty around the use of Pb isotopes for sourcing tin objects, it is now possible to contextualize the Uluburun tin ingots more securely within the metallurgical systems of the Central Taurus-Cilicia-Amanus axis. Recent scholarship has shown that tin production in the South-Central Taurus region had taken place at a scale not previously anticipated. Two parallel production systems appear to have been in place serving elite and common consumption networks via markedly different technologies. The South-Central Taurus and Cilician cities served as important components of maritime and terrestrial metal distribution around the eastern Mediterranean, providing a range of metals from a single geographical region.

Interwoven traditions in Bell Beaker metallurgy: Approaching the social value of copper at Bauma del Serrat del Pont (Northeast Iberia).

Debates on early metallurgy in Western Europe have frequently focused on the social value of copper (between utilitarian and symbolic) and its purported role in the emergence and consolidation of hierarchies. Recent research shows that generalisations are increasingly untenable and highlights the need for comparative regional studies. Given its location in an intermediate area, the early metallurgy of Northeast Iberia provides an interesting case in point to explore the interaction between the well-characterised traditions of southern Iberia and southern France during the 3rd and 2nd millennia BCE. Here the analytical study of seven Bell Beaker (decorated and undecorated) vessels reused as crucibles at Bauma del Serrrat del Pont (Tortellà, Girona) are presented. We employed pXRF, metallography, SEM-EDS and lead isotope analyses. The results show evidence for copper smelting employing a remarkable variety of ore sources, including Solana del Bepo, Turquesa and Les Ferreres mines, and an extra unknown area. The smelting vessels were manufactured using the same clay, which contained both mineral and organic inclusions. Our results are discussed with reference to all the evidence available for metals and metallurgy in the Northeast, and more broadly in comparison to southern Iberia and southern France, with special emphasis on issues of production organisation and social complexity. Taken together, our results support the notion that copper metallurgy played a predominantly utilitarian role in Bell Beaker societies and highlight idiosyncratic aspects of the metallurgical trajectory in the Northeast. Differences between territories challenge unilinear explanations of technological and social development after the introduction of metallurgy. Separate trajectories can only be explained in relation to area-specific socio-cultural and environmental factors.

Geochemistry and Pb isotopic proof for sources of heavy metal(loid)s in Late Cretaceous sandstones from Eastern Pontides (NE Turkey)

Upper Cretaceous sedimentary rocks are widely exposed around Trabzon, Giresun and Gümüşhane in the eastern Pontides. The sedimentary rocks are mainly composed of sandstones and marls, and the thicknesses of these rocks range from 170 to 400 m. This paper focused on Late Cretaceous sandstones of Trabzon, Giresun and Gümüşhane regions to identify the concentrations, sources, deposition environment and conditions of certain heavy metal(loid)s (Zn, Pb, Cu, Ni, As, Co, Mo and V). Enrichment factor (EF), geo-accumulation index (Igeo), Pollution index (Pi), Pollution load index (Pln), Pb isotope and multivariate statistical analysis were performed to elucidate the pollution levels and sources. In general, the evaluation indices exhibited that the sandstones were moderately polluted by As in the Trabzon area, and strongly polluted by Ni and As, moderately polluted by Co and V in the Giresun and Gümüşhane areas. The results of multivariate statistical analyses indicated that As and partly Pb might be originated from anthropogenic sources, whereas other metals were derived from geogenic origin. Lead isotopic analysis demonstrated two characterized signatures of the pollution sources in the sandstones, one related to geogenic origin and the other to coal, gasoline and pesticides. The sandstones were deposited in transition—marine environment under oxic—weak oxic conditions and paleoclimatic conditions ranged from arid to moist during Late Cretaceous period.

Sending Laurion Back to the Future: Bronze Age Silver and the Source of Confusion

Silver-bearing lead ores at Laurion in Attica were considered to have been first exploited with the introduction of coinage sometime around the birth of Classical Greece. However, in the late 20th century this chronology was radically revised earlier, to the Bronze Age, largely supported by lead isotope analyses (LIA). Here, we acknowledge that lead and silver metallurgy emerged from the earliest times but we propose that any correlation between these metals in the archaeological record is not a consequence of a geological association between lead and silver in ores such as galena until the middle of the first millennium BCE. We suggest that ancient metallurgists recognised that silver minerals (such as horn silver) dispersed in host rocks could be concentrated in molten lead and that LIA signatures of Bronze Age silver artefacts reflect the use of exogenous lead to extract silver, perhaps applying processes similar to those used to acquire silver in Bronze Age Siphnos. We further propose that lead from Laurion used for silver extraction resulted in the inadvertent transfer of its LIA signature (probably aided by roving silver prospectors) to silver objects and metallurgical debris recovered around the Aegean. New compositional analyses for the Mycenaean shaft-grave silver (c. 1600 BCE) support these conclusions. We believe that reverting to the mid-first millennium BCE for the first exploitation of silver from argentiferous lead ores is consistent with the absence of archaeological evidence for centralised control over Laurion until the Archaic period, the paucity of lead slag associated with silver-processing debris at Bronze Age sites, the scarcity of silver artefacts recovered in post-shaft grave contexts at Mycenae and throughout the Early Iron Age Aegean, the few Attic silver coins with LIA signatures consistent with Laurion until after 500 BCE and a single unambiguous mention of silver in the Linear B texts.

Lead Isotope Analysis of Geological Native Copper: Implications for Archaeological Provenance Research in the North American Arctic and Subarctic

The Indigenous inhabitants of Arctic and Subarctic North America had been using native copper for several centuries prior to sustained interaction with Europeans beginning in the 18th century. The connection, if any, between the use of copper in these two adjacent regions is, at present, unclear. The ability to determine the source of native copper artifacts found in greater northwestern North America would inform on the movement of copper via trade and exchange between, and aid in understanding the innovation and diffusion of native copper metallurgy among, ancestral Dene and Inuit People. This paper provides the results of a Lead Isotope Analysis (LIA) pilot study examining Pb isotope ratios of native copper samples from multiple locations in the northern regions of North America. The results from this preliminary study indicate some overlap in Pb isotope ratios between Arctic and Subarctic sources of native copper, and these nonetheless record distinct isotope signatures relative to those associated with other North American native Cu deposits.

Lead provenance for medieval decorated tile glazes from Brittany and Anjou (13th-14th c.)

Medieval pavements composed of lead-glazed tiles decorated with a variety of techniques continue to inspire questions about the organisation of glaze manufacture, and the supply and origin of lead materials. The tiles analysed in this study are from SuscinioI (a 13th-century pavement) and SuscinioII (a 14th-century pavement), at the Château of Suscinio in Brittany, and also from the 14th-century pavement at the fortified manor house in Brain-sur-Allonnes, Anjou. Lead isotope analysis (LIA) was used to examine samples from 44 lead-glazed tiles, 29 of which are transparent, while 15 are tin-opacified (an exogenous technique in these regions during this period). Five out of the six LIA groups thus identified favour site-specific supply networks, while results for the remaining group, LIA5, indicate a multi-site supply network. After combining LIA results with archaeological and historical data, the most likely provenance for the lead materials in LIA5 is Derbyshire, in the British Isles. Both the importation of ready-to-use glazing mixtures and the use of lead from neighbouring mines can now therefore be discounted as plausible hypotheses for the production of the tin-opacified lead-glaze tiles analysed in this study.

Sensitivity and High-Precision Lead Isotopic Analysis by Multicollector Inductively Coupled Plasma Mass Spectrometry Based on Liquid Spray Dielectric Barrier Discharge Plasma-Induced Chemical Vapor Generation

Sensitivity and High-Precision Lead Isotopic Analysis by Multicollector Inductively Coupled Plasma Mass Spectrometry Based on Liquid Spray Dielectric Barrier Discharge Plasma-Induced Chemical Vapor Generation

Lead Isotopic Characteristics and Metal Sources for the Jewelry in the Medieval Rural Settlements from the Suzdal Region (Kievan Rus’)

The article considers the results of the study of lead isotope composition of 38 non-ferrous artifacts discovered at medieval rural sites of the Suzdal Region (Kievan Rus’). The copper-alloy, silver and pewter artifacts were compared with reference data from geographically and temporally diverse medieval artifacts and ore deposits and revealed differing source regions and supply networks within and between metal types. The identification in some cases was difficult due to the conformity of the lead isotopic composition of deposits of some regions. The copper-alloys, represented mostly by crosses made of high-tin bronze, show close isotopic parallels to contemporary copper alloys from Southern Scandinavia, Westphalia and Lower Saxony. Since the copper alloys contain significant quantities of lead, this lead may have entered the metal by alloying with lead-tin alloys, by smelting mixed copper-lead ore, or through haphazard alloying with lead. The lead isotope ratios for nearly all copper alloys are consistent with deposits in Cornwall and Devon and remobilized ore from the Rhenish Massif. For silver and lead-tin alloy objects, lead isotope analyses point to wide ranging sources. Most silver objects are consistent with mid-to-late 10th century silver stocks circulating in the Baltic area and 10th century Volga-Bulgar silver dirham imitations probably representing mixtures of 9th-10th century Islamic silver. The silver shows a heavy reliance on 10th century mixed stocks and there are little indications of Central and Western European silver, which was common in the 11th century Baltic region. The pewter and lead, however, indicate other sources. Lead isotope ratios are consistent with sources connected to Mediterranean and Baltic networks, some being consistent with sources in England, but it is possible that the lead found in some pewter objects could come from the Olkusz lead district in southern Poland.

Identification of source mine using sulfur, mercury, and lead isotope analyses of vermilion used in three representative tombs from Kofun period in Japan

Vermilion, a precious red pigment that was used in ancient times, was believed to protect the dead from evil beings and was thus used in burial facilities in China and Japan. Vermilion was used frequently in tumuli in Japan during the expansion of the Yamato kingship (third to sixth centuries AD)—named the Kofun period. Until recently, the cinnabar used in tumuli in Japan was thought to have been imported from China, but evidence of its Japanese origin is gradually emerging. The purpose of this study is to evaluate the usefulness of S, Hg, and Pb isotope analyses for identifying the origin of the vermilion used in these tombs. Therefore, the S, Hg, and Pb isotope ratios of vermilion collected from three tumuli from the early Kofun period, namely, Sakurai-Chausuyama, Kurozuka, and Tenjinyama (which were built in the main area of the ancient Yamato kingship), were compared with those of cinnabar from the Yamato Mercury, Niu, and Suii mines in Japan and the Wanshan and Qingtongguo mines in China to identify the source of the vermilion. Each isotope indicates multiple possibilities about the origin of the vermilion used in each tumulus. Nonetheless, with the three isotopes considered at the same time, the results indicate that the red pigments from the Sakurai-Chausuyama tumulus come from the Yamato Mercury Mine, whereas the vermilion used in the Kurozuka and Tenjinyama tumuli is from the Niu Mine. Therefore, although single isotope analysis can be useful as a first approximation of the source mine of vermilion, analysis of all three isotopes yields considerably more accurate results. On the basis of these three isotope analysis methods, research on the distribution of ancient vermilion is expected to proceed from the identification of the origin of the vermilion used in the abovementioned ruins.

Copper production and supra-regional exchange networks – Cu-matte smelting in the Balkans between 2000 and 1500 BC

The Balkan Peninsula played a crucial role for the introduction of metallurgy during the Copper Age and numerous archaeometallurgical examinations have delivered highly interesting insights on this topic. However, there is a lack of systematic analytical research on copper ore smelting and metal exchange for the later Bronze Age. In this paper we focus on the first archaeometallurgical results of slags from the sites Ružana, Trnjane and Čoka Njica, Eastern Serbia, complimented by the discussion of XRF and lead isotope analyses carried out on 28 copper-based artefacts. Importantly, radiocarbon dating from these sites points to copper production already being undertaken at the end of the Early Bronze Age (19th–18th centuries BC), more than 500 years earlier than previously assumed. This enables us to investigate the flow of metal during the 1st half of the 2nd millennium BC. The analyses of the metallurgical slags indicate a copper matte smelting process in small open pit furnaces and the use of local sulfidic copper ore sources. The fact that these intensive smelting activities in Eastern Serbia can be paralleled with the early production hotspots in central Europe e.g. on the Hochkönig (Mitterberg mining areas) sheds new light on the development of copper based metallurgy in Europe. At the same time, the evidence from Eastern Serbia shows that this area was a source of raw material for copper and bronze alloys providing a regional and supra-regional perspective. Furthermore, our analyses revealed the remarkable result, that by the start of the Middle Bronze Age (ca. 1700 BC) copper from the Northern Italian mining areas in the Trentino region also reached the western and central Balkans.

The prestigious tin–lead horse fittings in the Warring States Period: Evidence from funerary artefacts of a Warring States Tomb at Shouxian, Anhui

Tomb M25 of the Xijuan cemetery at Shouxian was identified as a Cai elite tomb dated to the fifth century bce. From this tomb, 182 metal items were unearthed, and two‐thirds of them were found made with Sn‐Pb alloy via portable X‐ray fluorescence (pXRF) and scanning electron microscopy with energy‐dispersive spectroscopy (SEM‐EDS) analyses. Lead isotope analysis (LIA) revealed that leaded bronze and Sn‐Pb alloy did not share the same source of lead. The isotopic feature of tin–lead objects is varied from most reported Early–Middle Warring States bronzes from the Nanyang‐Huaihe area, but coincides with artefacts from the Chu state core area in the Jianghan basin as well as some Zeng state artefacts from the Suizhou area. A general review of the Early–Middle Warring States Chu tombs shows that two types of gold‐foiled tin–lead horse fittings from tomb M25 were also present in almost all high elites tombs, but were barely found in those of the lower elites. It is argued that these horse fittings were prestigious artefacts and made with tin–lead raw materials from south China. They might be distributed as finished artefacts or raw materials via a gift‐giving system controlled by the Chu court.

Transformative copper metallurgy in Chalcolithic Cyprus: a reappraisal

The extraction and smelting of the rich copper ore deposits of Cyprus and the manufacture of copper objects on the island are thought to have begun during the Philia phase (c. 2400–2200 BC). Here, the authors present the results of lead isotope analysis undertaken on Late Chalcolithic (2900–2400 BC) metal objects from the site of Chlorakas-Palloures. The results facilitate a reassessment of the timing of the start of transformative copper technologies on Cyprus and the re-evaluation of contemporaneous copper artefacts from Jordan and Crete previously suggested to have been consistent with Cypriot ores. They conclude that there is no compelling evidence for transformative metallurgy in Chalcolithic Cyprus.

Tracking Roman lead sources using lead isotope analysis. A case study from the imperial rural estate at Vagnari (Puglia, Italy)

Recent studies have utilised isotopic analysis for an understanding of the supply sources of lead to major Roman cities in Italy to good effect. Far less attention has been focused on contemporary rural sites in Italy or on the evidence for lead ore sources and the use and processing of lead in such locations. Rather than the more common focus on the isotopic analysis of lead pipes and ingots, this study concentrates on the lead processing and recycling debris, as well as the finished utilitarian objects, excavated in the central village of an imperial estate at Vagnari in south-east Italy. The archaeological and isotopic evidence indicates that the source of lead used in the production of implements here was not uniform, rather the ores stem from various regions within the Roman empire ranging from Italy, Spain, and Greece, to France or possibly Britain.