Natural attenuation of antimony and arsenic in soils at the abandoned Sb-deposit Poproč, Slovakia

Abstract

This contribution investigates the natural attenuation of arsenic (As) and antimony (Sb) in highly contaminated soils at the abandoned Sb-deposit Poproč in eastern Slovakia. The studied soils were identified as technosols with pH values of 3.5–7.0 and high metal and metalloid load: antimony, arsenic, lead, and zinc up to 5757, 2484, 683, and 407 mg/kg, respectively. These toxic elements occur in the soils mainly as constituents of secondary minerals, which are products of sulphide oxidation. Bulk correlation between Fe and As is weak (p\u2009>\u20090.05), but inspection of micro-X-ray fluorescence maps shows that the secondary iron oxides are always associated with elevated As. Electron microprobe (EMP) and micro-X-ray diffraction analyses showed significant chemical and mineralogical heterogeneity of the secondary minerals, with wide variations of their Fe/Sb ratio and occasionally elevated Ca and Pb (>\u20095 wt%). The most common secondary minerals are goethite (α-FeOOH) with concentrations of Sb up to 3.14 wt% and As (1.29 wt%) and tripuhyite (FeSbO4) with increased content of As (1.14 wt%). Sb-rich secondary phases were identified as valentinite/senarmontite (Sb2O3), cervantite (Sb2O4), and a pyrochlore-group mineral stibiconite. High Sb phases with increased concentrations of Ca (up to 6.48 wt%) or Pb (20.78 wt%) were identified as stibiconite (EMP). This study shows that the secondary mineralogy in naturally attenuated contaminated soils and in Sb-containing tailings is identical. Hence, such tailings achieve their final state with respect to the Sb minerals within decades and are unlikely to change further.