Mixed lead sources in tin metal: Implications for using lead isotopes to study tin artifacts

Methods for provenancing copper, lead, and silver using the isotopic composition of lead are well-established. Lead isotope analysis holds promise for the study of tin metal as well, as long as one accounts for the U-Th-Pb systematics of cassiterite (SnO₂) and chaîne opératoire of tin production. Although Precambrian cassiterite may contain 10s of ppm Pb or more (predominantly radiogenic ²⁰⁶Pb), Phanerozoic examples typically contain only a few parts per million Pb. However, all but one of the 133 raw tin ingots excavated from European Bronze Age shipwrecks contains more Pb than could have come from cassiterite alone, as do six of the twelve analyzed tin objects interpreted to have been derived from the ores of southern Africa. Accordingly, almost all tin objects must contain Pb from external cassiterite sources and interpretation of LIA must account for this contamination. The nature of the contaminant (sulfides, U-Th-bearing minerals, silicates) can be inferred from patterns in Pb concentration and LI values. The 3 major sources of Pb that can typically be identified in tin artifacts are original Pb from the tin ore, radiogenic Pb produced in-situ due to U decay, and external Pb added during the cassiterite smelting and ingot production. As cassiterite has high U/Pb but low Th/Pb, the ²⁰⁸Pb/²⁰⁴Pb may be representative of the initial Pb incorporated in the mineral. This is assuming either that no external Pb is added during the ore processing or that the added Pb is from coeval sulfides from the same Pb ore provenance. In such cases 208Pb/204 Pb can be used to estimate a Pb model age, which in turn can be used for provenance estimate of the ingots. If the addition of Pb is from U-Th-mineral contaminants to the ore concentrate, then this will also increase ²⁰⁸Pb/²⁰⁴Pb and point to erroneously young model Pb ages. In such cases, the problem would be evident in positively correlated values of ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb. If Pb concentrations are above a certain threshold (approximately 5 ppm). LIA typical common Pb isotope ratios will be clear indication that external, non-cassiterite Pb, is added to the tin artifact. This tin could be from impurities in the ore (e.g., inclusions in cassiterite, impurities in the ore concentrate, or added during ore smelting and/or metal processing. Overall, elevated Pb concentrations accompanied with non-radiogenic Pb isotopes typical for common Pb, is a clear indication that significant amount of external (contaminant) Pb is added to the tin artifact.