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When and why did the Phoenicians initiate long-term connections between the Levant and western Europe? This is one of the most hotly debated questions in ancient Mediterranean history and cultural research. In this study, we use silver to answer this question, presenting the largest dataset of chemical and isotopic analyses of silver items from silver hoards found in Phoenician homeland sites. Intertwining lead isotope analysis of silver items with precise archaeological context and chronology, we provide analytical evidence for the onset of Phoenician westward expansion. We suggest that the quest for silver instigated a long, exploratory phase, first in Anatolia (Asia Minor) and Sardinia, and subsequently in the Iberian Peninsula. This phase preceded the establishment of sustainable, flourishing Phoenician colonies in the West by over a century. In so doing, our results buttress the “precolonization” theory, accord it a firm chronological framework, and demonstrate that the quest for silver (and probably other metals) was an incentive for Phoenician westward expansion. Furthermore, our results show that the Phoenicians introduced innovative silver production methods to historic Europe.

The Wusihe carbonate-hosted Zn-Pb deposit (3.7 Mt. Zn + Pb at a grade of 8.6% Zn and 2.0% Pb) is the largest deposit in the Dadu River Valley district of the Sichuan-Yunnan-Guizhou metallogenic province of southwest China. Three types of orebodies occur: (1) stratiform, banded and lamellar, within dolomite of the Neoproterozoic Dengying Formation; (2) vein type; and (3) breccia type. Four stages of mineralization are distinguished: (i) pyrite stage, (ii) pyrite-pyrrhotite-galena-sphalerite-bitumen stage, (iii) sphalerite-galena stage, and (iv) bitumen-calcite stage. Sphalerite and galena from stages II and III show δ34S ranges from +7.1 to +9.7‰ and +9.1 to +13.1‰, respectively. High-precision in situ lead isotope analyses of sulfides show 208Pb/204Pb, 207Pb/204Pb, and 206Pb/204Pb ratios of 37.938 to 38.336, 15.579 to 15.682, and 17.951 to 18.195, respectively, which suggest a mixing of lead from the basement and the host rocks. Rb-Sr isotope analyses for six sphalerite samples of stage II yielded an isochron age of 411 ± 10 Ma (MSWD = 1.4). Combining all available ore geology and geochemical data, together with fluid inclusion data reported previously, we suggest that the Wusihe deposit is a Mississippi Valley-type (MVT) deposit.

Bullet projectiles are often found in shooting crime scenes and can help identify the cartridges used in shooting events. The most conclusive way to link a fired projectile to a firearm is by identifying the unique markings of the barrel on the projectile or case. But in circumstances where the investigation of striation marks is impossible, lead isotope ratio signature analysis of projectile fragments can facilitate building the linkage of the suspect, the cartridge used and the victim. This work presents a shooting incident happened in a hunting field, where a hunting guide was shot to death. A tiny lead projectile fragment was collected from the victim’s head. Pb isotope ratios measured by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) were used to make comparisons between the fragment and the shots seized from two suspects. Additionally, a reference dataset comprising 50 lead bullet projectiles from various manufacturers was characterized using LA-MC-ICPMS. The evaluation of the comparison was carried out by multivariate likelihood ratio (LR) computations based on the reference dataset. The lead isotope ratio and likelihood ratio evaluation methods helped infer the source of the fragment and were highly supportive in the shooting incident investigation. •Pb isotope ratio signature was used for projectile discrimination in a shooting incident investigation.•Likelihood ratio calculations were carried out for forensic interpretation of isotopic ratio for bullet lead.•Pb isotope ratio signature and likelihood ratio calculation help to identify the shooter in a shooting incident.

The Hatu gold deposit is the largest historical gold producer of the West Junggar, western China, with an Au reserve of about 62 t. The orebodies were controlled by NE-, EW-, and NW-trending subsidiary faults associated with the Anqi fault. This deposit exhibits characteristics typical of a fault-controlled lode system, and the orebodies consist of auriferous quartz veins and altered wall rocks within Early Carboniferous volcano-sedimentary rocks. Three stages of mineralization have been identified in the Hatu gold deposit: the early pyrite-albite-quartz stage, the middle polymetallic sulfides-ankerite-quartz stage, and late quartz-calcite stage. The sulfur isotopic values of pyrite and arsenopyrite vary in a narrow range from − 0.8‰ to 1.3‰ and an average of 0.4‰, the near-zero δ 34 S values implicate the thorough homogenization of the sulfur isotopes during the metamorphic dehydration of the Early Carboniferous volcano-sedimentary rocks. Lead isotopic results of pyrite and arsenopyrite ( 206 Pb/ 204 Pb = 17.889–18.447, 207 Pb/ 204 Pb = 15.492–15.571, 208 Pb/ 204 Pb = 37.802–38.113) are clustered between orogenic and mantle/upper crust lines, indicating that the lead was mainly sourced from the hostrocks within the Early Carboniferous Tailegula Formation. The characteristics of S and Pb isotopes suggest that the ore-forming metals of the Hatu orogenic gold deposit are of metamorphogenic origin, associated with the continental collision between the Yili-Kazakhstan and Siberian plates during the Late Carboniferous.

The analysis of isotope ratios of lead in the mushrooms and soil, where they were grown, assisted with a principal component analysis, offered a new perspective for understanding possible chemical environment in a real setup of those compartments. The content of lead and its isotope compositions were determined in soil samples and mushroom Macrolepiota procera from unpolluted area of Mountain Goč, Serbia. Sequential extraction procedure based on the Commission of the European Community Bureau of Reference (BCR) was applied on soil samples in order to determine the distribution of lead in the labile and un-labile fractions of the soil. Caps and stipes of mushrooms were subjected to microwave acid-assisted digestion prior to measurements by inductively coupled plasma quadrupole mass spectrometer for determination of lead content and lead isotope ratios. Information about the chemical fractionation of Pb in soil, Pb isotopic data from soil fractions and fruiting bodies allowed a more detailed insight on the uptake mechanisms. Lead was predominantly associated with reducible fraction (~ 60%). Only its small portion (∼ 1%) was present in the exchangeable and acid-extractable fractions suggesting the low mobility of Pb. Lead isotope analysis revealed the presence of anthropogenic lead in the surface soil. Significant lower 206 Pb/ 207 Pb compared with other fractions was found in exchangeable and acid-soluble fraction (1.331 ± 0.010), which corresponds to the isotope ratio of European gasoline. The highest 206 Pb/ 207 Pb ratio was observed in reducible fraction (1.162 ± 0.007), while in oxidizable and residual fraction, those values were similar (1.159 ± 0.006 and 1.159 ± 0.004, respectively). Distinction of exchangeable and acid-extractable fractions from others was also confirmed, for the first time, by principal component analysis. The analysis of four isotope ratios ( 206 Pb/ 207 Pb, 208 Pb/ 206 Pb, 206 Pb/ 204 Pb, and 207 Pb/ 204 Pb) indicated that the analyzed M. procera accumulates lead from the first two fractions of topsoil layers.

Metal(loid)s pose a significant hazard due to inherent toxicity. Individuals are particularly exposed to metal(loid)s in soil through direct or indirect contact. Identifying metal(loid) sources in soil is required for exposure mitigation to anthropogenic metal(loid)s, while metal(loid)s are natural constitutes of soil. Metal(loid) concentrations and Pb isotopes were determined in residential soil profiles impacted by a Zn smelter to distinguish the anthropogenic effect from natural levels. One hundred sixty-nine core soil samples were collected from depths down to 5.5 m below ground level at 19 sites and were divided into Zn-Cd-As- and As-contaminated groups based on the worrisome level (WL) of soil contamination. The Zn-Cd-As-contaminated group ( n  = 62) was observed at depths < 1 m, showed high Zn levels (mean of 1168 mg/kg) and Cd and As frequently exceeding WLs, and had low 206 Pb/ 207 Pb ratios close to the Zn smelter. In contrast, the As-contaminated group ( n  = 96) was observed at depths > 1 m, did not have other metals exceeding WLs, and showed a wide range of 206 Pb/ 207 Pb ratios far away from the Zn smelter. The results indicated that the pollution sources of Zn-Cd-As- and As-contaminated soils were fugitive dust emissions from smelter stacks and geology, respectively. The metal(loid)s in host rock set geochemical baselines in soil profiles, while smelting activities affected the upper layers over 50 years. This study demonstrated the effectiveness of utilizing the vertical distribution of metal(loid) concentrations and Pb isotopes in soil profiles for distinguishing between anthropogenic and geogenic origins, in combination with baseline assessment.

The rapid development of livestock and poultry industry in China has caused serious environment pollution problems. To understand the heavy metals accumulation and identify their sources, 7 heavy metals contents and lead isotope ratios were determined in 24 soil samples from vegetable fields irrigated with swine wastewater in Dongxiang County, Jiangxi Province, China. The results showed that the concentration of Cr, Ni, Cu, Zn, As, Cd and Pb in the swine wastewater irrigated vegetable soils varied from 38.5 to 86.4, 7.57 to 30.6, 20.0 to 57.1, 37.5 to 174, 9.18 to 53.1, 0.043 to 0.274 and 12.8 to 37.1 mg/kg, respectively. The soils were moderately to heavily polluted by As, moderately polluted by Cr, Ni, Cu, Zn and Cd, and unpolluted to moderately polluted by Pb. Sampling soils were classified as moderately polluted according to the Nemerow comprehensive pollution index. Lead isotope and Principal Component Analysis (PCA) analysis indicated that swine wastewater irrigation and atmospheric deposition were the primary sources of the heavy metals.

The rich copper ore deposits in the eastern Alps have long been considered as important sources for copper in prehistoric central Europe. However, the role that each deposit played is not clear. To evaluate the amount of prehistoric copper produced from the various mining regions, we attempted to link prehistoric metal artefacts with copper ores based on the geochemical characteristics of the ore deposits that were exploited in ancient times. Alongside the usage of ores as shown by the finished products, the production aspects, the quantity and variation over time must also be considered. Recent archaeological investigation has allowed these datasets to be combined in order to show the importance of one of the largest Bronze Age mining fields in Europe. More than 120 ore samples from the well-known mining regions of Mitterberg, Viehhofen, and Kitzbühel were analysed for lead isotope ratios and trace element concentrations. These results were combined with analytical data generated by previous archaeometallurgical projects in order to compile a substantial database for comparative studies. In the Early Bronze Age, most metal artefacts were made of copper or bronze with fahlore impurity patterns, and most examples from this period match the fahlore deposits in Schwaz and Brixlegg. At the end of the Early Bronze Age, a new variety of copper with low concentrations of impurities appeared. The impurity patterns of these examples match the ores from the Mitterberg region. Later, in the Middle Bronze Age, this variety of copper almost completely replaced the fahlore copper. In the Late Bronze Age, the exploitation of the ores changed again and copper with a fahlore signature reappeared. The reason for the renewed copper production from fahlores might have been a decline of the chalcopyrite mines. But it was more likely due to the fact that the rising demand for copper could no longer be met by the chalcopyrite mines alone. The examples from the Early Iron Age show no fundamental changes in metal composition. The copper metallurgy in the Early Iron Age is based on the traditions of the Late Bronze Age. Die reichen Kupferlagerstätten in den Ostalpen werden seit langem als wichtige Rohstoffquellen für das Kupfer im prähistorischen Europa betrachtet. Dennoch war bislang nicht so klar, welche Rolle einzelnen Lagerstätten in diesem Zusammenhang zukam. Um die Bedeutung der Kupferproduktion in einzelnen Bergbaurevieren besser zu verstehen zu können, wurde nach der Verbindung zwischen Metallartefakten und der geochemischen Charakteristik einzelner in prähistorischer Zeit abgebauten Lagerstätten gesucht. Doch neben den Aspekten der Nutzung von Erzkörpern, welche durch die Endprodukte angesprochen sind, müssen auch Produktionsfragen, etwa nach der Gesamtmenge der Kupferproduktion und ihrer zeitlichen Variation, beachtet werden. Jüngste archäologische Untersuchungen erlauben eine präzise Kombination beider Datengrundlagen. Sie ermöglichen neue Einblicke in die Bedeutung einer der größten Bergbaulandschaften der Bronzezeit in Europa, des Mitterbergs. Mehr als 120 Erzproben der gut bekannten Bergbaureviere Mitterberg, Kitzbühel und Viehhöfen wurden anhand ihrer Pb-Isotopen-Verhältnisse und Spurenelementmuster untersucht. Diese Ergebnisse wurden mit bisherigen analytischen Daten archäometallurgischer Projekte kombiniert und so eine substantielle Basis für Vergleichsstudien erreicht. In der Frühbronzezeit bestanden die meisten Metallobjekte aus einem Kupfer mit typischer Fahlerzsignatur. Es passt gut zu den Fahlerzlagerstätten von Schwaz und Brixlegg. Am Ende der Frühbronzezeit erschien eine neue Kupfervarietät mit geringeren Spurenund Nebenelementanteilen. Dieses Spurenelementmuster stimmt bestens mit den Erzen der Mitterberger Bergbauregion überein. In späterer Zeit verdrängte diese Kupfersorte gänzlich das Fahlerz-Kupfer. In der späten Bronzezeit änderte sich die Ausbeute der Erze erneut und Fahlerzkupfer-Signaturen erschienen erneut. Der Grund für die erneute Ausbeute des Fahlerzkupfers könnte ein Rückgehen der Kupferkiesproduktion sein, wahrscheinlicher ist aber, dass die Kupferkiesproduktion den Bedarf an Kupfer allein nicht mehr zu decken vermochte. Die Funde der frühen Eisenzeit zeigen keine fundamentalen Änderungen in der Metallzusammensetzung mehr. Die Kupferproduktion der frühen Eisenzeit basiert im Wesentlichen auf den Traditionen der Spätbronzezeit.

This study presents a comprehensive archaeometallurgical analysis of 21 bronze rings recovered from the Nanhai No. I shipwreck, a remarkable historical site dating back to the Southern Song Dynasty (1127–1279 AD). The shipwreck, located in the South China Sea, has provided a unique window into the trade and contraband activities of the time. Through a meticulous examination of their composition, microstructure, trace elements, and lead isotopes by SEM, metallography, MC-ICP-MS, and ICP-AES, we unveil the manufacturing techniques, material origins, and the latent details within these seemingly ordinary artifacts. These bronze rings share high-lead content with other Song Dynasty bronzes. They are classified into three groups based on their copper and lead composition, with one group aligning with historical records, hinting at pre-prepared complex alloys designed for specific purposes. The stability of trace elements and lead isotopes in the rings indicates Guangdong region as the most probable source of the raw materials. These findings lead to the speculation that Nanhai No. I may have docked at a Guangdong port to replenish its cargo, including contraband goods such as bronze rings, before departing the Song Dynasty’s territory with minimal scrutiny. In summary, this research enhances our understanding of ancient trade and smuggling practices and showcases archaeometallurgy’s potential in unveiling the untold stories behind historical artifacts.

A large number of Yue style bronzes with regional cultural characteristics were unearthed in Hunan, which is of great significance for studying the cross-regional circulation of bronze technology and metal resources in the south of the Yangtze River during the Late Bronze Age (8 ~ 5 C. BCE) in China. In this study, 30 Yue style bronzes and 3 Chu style bronzes unearthed from five regions in Hunan Province were analyzed for chemical composition, metallography and lead isotopes. The results show that the alloy materials of Hunan Yue style bronze ware are diverse. The containers are mainly leaded tin bronze, with both tin bronze and copper. The weapons or tools are mostly tin bronze, and the alloy composition is primarily tin. The lead isotope ratio analysis results showed three main ore sources: polymetallic deposits in the Nanling Mountains, the eastern Hubei-northern Jiangxi metallogenic belt and the western Henan Qinling-Dabie metallogenic belt. The extensive source of minerals reflects the frequent trade of metal resources between Yue people and the Chu state, which is not only the economic basis for the close relationship between Hunan Yue people and Chu State but also an important driving force for the southward expansion of the Chu state and national integration in Hunan.