Legacy of multiple heavy metal(loid)s contamination and ecological risks in farmland soils from a historical artisanal zinc smelting area.

Farmland soil contamination of heavy metal(loid)s (HM) derived from smelting activities is a global concern, owing to its potential threat for human health through food chain. This study aims to evaluate total contents and bioavailability of HMs (Pb, Zn, Tl, Cd, Cu, As, Ag, Co, Cr and Ni) in farmland soils distributed over ten different villages from a former artisanal zinc smelting area in the northwest Guizhou province, China. The results showed that most of the studied soils still exhibited exceptionally high enrichment of Pb, Zn, Cd and As. High levels of bioavailable HMs were also observed in some samples, which may enter the human food chain through agricultural activities. Further analyses by Scanning Transmission Electron Microscopy - Energy Dispersive Spectroscopy (STEM-EDS), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) showed the presence of Zn smelting by-products such as Fe oxides, ZnO and PbSO4 even in nanoscale particles retained by the soils. Elemental mapping by EDS confirmed a close association of the studied HMs with the smelting waste particles. All these results signify that high levels of HM-contamination from historical artisanal zinc smelting activities still persist and threaten the health of local residents, despite the fact that the major industrial-derived-contamination period ended >15 years ago. Our findings highlight pivotal concerns in similar artisanal-smelting-affected farmland soils of suspected contamination, due to less-expected toxic elements such as Tl, which may cause high ecological health risks.