Identifying the source of Zn in soils around a Zn smelter using Pb isotope ratios and mineralogical analysis

The contribution by anthropogenic sources to abnormally high Zn concentrations in soils with naturally abundant Zn was investigated at a contaminated site surrounding a Zn smelter in eastern Korea. Nineteen soil samples were collected within a 2 km radius of the smelter, and analyzed for metal concentrations and Pb isotope ratios using an inductively coupled plasma-optical emission spectrometer and -mass spectrometer, respectively. Higher Zn concentrations in locations closer to the smelter implied that the smelter was the source of the Zn pollution. Lead isotope ratios (^206/207Pb) from soil samples assumed to be unaffected by the smelter were higher than those found in the contaminated area, suggesting that the raw materials of Zn concentrates (ZnS, sphalerites) and smelting by-products from the smelter with low ^206/207Pb ratios were the anthropogenic Zn source impacting the area. To verify this finding, the mineralogical forms of Zn found in the different soil fractions were investigated by X-ray diffraction analysis, scanning-electron-microscope energy-dispersive spectrometer analysis, and sulfur element analysis. Since approximately 50% of Zn concentrates have particle sizes less than 0.044 mm, the observation of sphalerites and elevated sulfur concentrations in the finer soil fraction (< 0.044 mm) provide substantial support to the hypothesis that the deposition of airborne Zn-containing dust from the smelter is responsible for the high Zn concentration in the area.