Application of Cu isotopes to identify Cu sources in soils impacted by multiple anthropogenic activities

Copper (Cu) is an important micronutrient for animals and plants, but it is toxic at high concentrations in soil. Soils adjacent to industrial areas would be subjected to severe Cu pollution. Identifying Cu sources in the surface environment is crucial for understanding their pollution level and fate. This study investigated Cu content, isotope composition of topsoils, and two soil profiles with varying levels of Cu contamination and related potential Cu sources in southwest China. The difference in Cu isotope compositions of tailing (1.29 ± 0.08 ‰), smelting fly ash (0.04 ± 0.03 ‰), coal (2.44 ± 0.09 ‰), coal-burning fly ash (0.34 ± 0.03 ‰), and geogenic soil (0.10 ± 0.03 ‰) enabled us to distinguish anthropogenic Cu from geogenic Cu. The plot of δ⁶⁵Cu and 1/Cu demonstrates that Cu of the polluted soils was from three end-members: the smelting fly ash, the vehicle exhaust, and the background soils. Based on the mass balance model, we calculated that the fly ash from smelting was the major anthropogenic source, contributing approximately 29 % of Cu contamination in soils, and the diesel exhaust was another important source, with a contribution rate of approximately 25 %. Additionally, soil profile results suggest that anthropogenic Cu could transport through soil profiles and influence Cu content and isotope signatures of subsurface soils, at least to a depth of ∼60 cm. Finally, our research indicates that Cu isotopes could be a promising tool for tracing industrial pollution, as significant Cu isotope fractionation would occur during the smelting process. Our research highlights the contribution of smelting and diesel exhaust to Cu contamination in the soils in a representative mining area. These findings serve as a scientific foundation for the development of policy for pollution control in industrial-affected regions.