Lead (Pb) isotopes provide valuable insights into the origin of Pb within a sample, typically allowing for reliable fingerprinting of their source. This is useful for a variety of applications, from tracing sources of pollution-related Pb, to the origins of Pb in archaeological artefacts. However, current approaches investigate source proportions via graphical means, or simple mixing models. As such, an approach, which quantitatively assesses source proportions and fingerprints the signature of analysed Pb, especially for larger numbers of sources, would be valuable. Here we use an advanced Bayesian isotope mixing model for three such applications: tracing dust sources in pre-anthropogenic environmental samples, tracking changing ore exploitation during the Roman period, and identifying the source of Pb in a Roman-age mining artefact. These examples indicate this approach can understand changing Pb sources deposited during both pre-anthropogenic times, when natural cycling of Pb dominated, and the Roman period, one marked by significant anthropogenic pollution. Our archaeometric investigation indicates clear input of Pb from Romanian ores previously speculated, but not proven, to have been the Pb source. Our approach can be applied to a range of disciplines, providing a new method for robustly tracing sources of Pb observed within a variety of environments.

The breccia-hosted epithermal Au-Ag deposit of Roşia Montană is located 7 km northeast of Abrud, in the northern part of the South Apuseni Mountains, Romania. Estimated total reserves of 214.91 million metric tons (Mt) of ore at 1.46 g/t Au and 6.9 g/t Ag (10.1 Moz of Au and 47.6 Moz of Ag) make Roşia Montană one of the largest gold deposits in Europe. At this location, Miocene calc-alkaline magmatic and hydrothermal activity was associated with local extensional tectonics within a strike-slip regime related to the indentation of the Adriatic microplate into the European plate during the Carpathian orogenesis. The host rocks of the magmatic complex consist of pre-Mesozoic metamorphosed continental crust covered by Cretaceous turbiditic sediment (flysch). Magmatic activity at Roşia Montană and its surroundings occurred in several pulses and lasted about 7 m.y. Roşia Montană is a breccia-hosted epithermal system related to strong phreatomagmatic activity due to the shallow emplacement of the Montana dacite. The Montana dacite intruded Miocene volcaniclastic material (volcaniclastic breccias) and crops out at Cetate and Cârnic Hills. Current mining is focused primarily on the Cetate open pit, which was mapped in detail, leading to the recognition of three distinct breccia bodies: the dacite breccia with a dominantly hydrothermal matrix, the gray polymict breccia with a greater proportion of sand-sized matrix support, and the black polymict breccia, which reached to the surface, contains carbonized tree trunks and has a dominantly barren clastic matrix. The hydrothermal alteration is pervasive. Adularia alteration with a phyllic overprint is ubiquitous; silicification and argillic alteration occur locally. Mineralization consists of quartz, adularia, carbonates (commonly Mn-rich), pyrite, Fe-poor sphalerite, galena, chalcopyrite, tetrahedrite, and native gold and occurs as disseminations, as well as in veins and filling vugs within the Montana dacite and the different breccias. The age of mineralization (12.85 ± 0.07 Ma) was determined by 40Ar-39Ar dating on hydrothermal adularia crystals from vugs in the dacite breccia in the Cetate open pit. Microthermometric measurements of fluid inclusions in quartz phenocrysts from the Montana dacite revealed two fluid types that are absent from the hydrothermal breccia and must have been trapped at depth prior to dacite dome emplacement: brine inclusions (32–55 wt % NaCl equiv, homogenizing at Th > 460°C) and intermediate density fluids (4.9–15.6 wt % NaCl equiv, Th between 345°–430°C). Secondary aqueous fluid inclusion assemblages in the phenocrysts have salinities of 0.2 to 2.2 wt percent NaCl equiv and Th of 200° to 280°C. Fluid inclusion assemblages in hydrothermal quartz from breccias and veins have salinities of 0.2 to 3.4 wt percent NaCl equiv and Th from 200° to 270°C. The oxygen isotope composition of several zones of an ore-related epithermal quartz crystal indicate a very constant δ18O of 4.5 to 5.0 per mil for the mineralizing fluid, despite significant salinity and temperature variation over time. Following microthermometry, selected fluid inclusion assemblages were analyzed by laser ablation-inductively coupled-plasma mass spectrometry (LA-ICPMS). Despite systematic differences in salinity between phenocryst-hosted fluids trapped at depth and fluids from quartz in the epithermal breccias, all fluids have overlapping major and trace cation ratios, including identical Na/K/Rb/Sr/Cs/Ba. Consistent with the constant near-magmatic oxygen isotope composition of the hydrothermal fluids, these data strongly indicate a common magmatic component of these chemically conservative solutes in all fluids. Cu, Pb, Zn, and Mn show variations in concentration relative to the relatively non-reactive alkalis, reflecting the precipitation of sulfide minerals together with Au in the epithermal breccia, and possibly of Cu in an inferred subjacent porphyry environment. The magmatic-hydrothermal processes responsible for epithermal Au-Ag mineralization at Roşia Montană are, however, not directly related to the formation of the spatially associated porphyry Cu-Au deposit of Roşia Poieni, which occurred about 3 m.y. later

The Celtic culture of Western Europe left magnificent gold objects, such as jewellery and weapons from nobility graves and hoarded coins, as well as field evidence of pre-Roman gold mining and metallurgical workshops that attest to the mining of local ores. This is the case of Central France where many precious metallic ores have been mined throughout the ages from the Prehistoric times onwards. One of the lingering problems in assessing the provenance of gold artefacts and coins is the lack of relevant data on the isotope geochemistry and mineralogy of ore sources. Forty gold ores samples were collected and studied from Limousin (French Massif Central), a very significant gold mining district from the Celtic times. Their Pb isotope compositions clearly show a local dichotomy i.e. two distinct groups of ores, one of Late Proterozoic to Early Paleozoic Pb model age and another associated to Variscan ages and consistent with field relationships, mineralogy and elemental analyses. The use of Cu and Ag isotopes, and their coupling with Pb isotopes, will refine the tracing of future metal provenance studies, but also highlight some metallurgical practices like deliberate metal additions to gold artefact or debasement of gold coins. The newly acquired Pb, Ag, and Cu isotopic data on gold ores improves our understanding of ore deposits geology and provide clarifications on the provenance of Celtic gold from this area and its economic importance.