Stable isotope fractionation of thallium as novel evidence for its geochemical transfer during lead‑zinc smelting activities

Thallium (Tl) is a highly toxic trace metal. Lead (Pb)‑zinc (Zn) smelting, which is a pillar industry in various countries, is regarded as one of the dominant anthropogenic sources of Tl contamination in the environment. In this study, thallium isotope data have been evaluated for raw material and a set of industrial wastes produced at different stages of Pb-Zn smelting in a representative large facility located by the North River, South China, in order to capture Tl isotope signatures of such typical anthropogenic origin for laying the foundation of tracking Tl pollution. Large variations in Tl isotopic compositions of raw Pb-Zn ores and solid smelting wastes produced along the process chain were observed. The ε²⁰⁵Tl values of raw Pb-Zn ores and return fines are −0.87 ± 0.26 and −1.0 ± 0.17, respectively, contrasted by increasingly more negative values for electrostatic precipitator dust (ε²⁰⁵Tl = −2.03 ± 0.14), lime neutralizing slag (ε²⁰⁵Tl = −2.36 ± 0.18), and acid sludge (ε²⁰⁵Tl = −4.62 ± 0.76). The heaviest ε²⁰⁵Tl (1.12 ± 0.51) was found in clinker. These results show that isotopic fractionation occurs during the smelting processes. Obviously, the lighter Tl isotope is enriched in the vapor phase (−3.75 ε²⁰⁵Tl units). Further XPS and STEM-EDS analyses show that Tl isotope fractionation conforms to the Rayleigh fractionation model, and adsorption of ²⁰⁵Tl onto hematite (Fe₂O₃) may play an important role in the enrichment of the heavier Tl isotope. The findings demonstrate that Tl isotope analysis is a robust tool to aid our understanding of Tl behavior in smelting processes and to provide a basis for source apportionment of Tl contaminations.