Contaminated soils of different natural pH and industrial origin: The role of (nano) iron- and manganese-based amendments in As, Sb, Pb, and Zn leachability

Highlights: • Soil natural pH affects the stability or functionality of immobilising agents. • Leaching of As significantly decreased in nZVI-treated soil in a wide range of pH. • Nano zero-valent iron as a perspective amendment for Sb immobilisation in soils. • Amorphous Mn oxide efficiently immobilised As at pH > 7. • Mineralogical investigations revealed different stages of nZVI transformation. Soils containing a large proportion of industrial waste can pose a health risk due to high environmentally available concentrations of toxic metal(loid)s. Nano zero-valent iron (nZVI) and amorphous manganese oxide (AMO) were applied as immobilising amendments (1 wt%) to soils with different industrial origin of As and Sb, and leaching of As, Sb, Pb, and Zn was investigated using a single extraction with deionised water. The different industrial impact was reflected in the mineralogy, chemical composition and pH of these soils. Water-soluble As ratios positively correlated with pH in all experimental treatments. A significant decrease of water-soluble As ratios was observed in all nZVI-amended soils (~65–93% of the control) except for one sample with the lowest solution pH. Nano zero-valent iron was also successful in Sb immobilisation (~76–90% of the control). Highly variable results were obtained for AMO, which only led to a decrease of water-soluble As in soils with solution pH of ≥7 (~70–80% of the control), probably due to lower stability of AMO in acidic conditions. In each case, nZVI was more efficient at decreasing water-soluble As ratios than AMO. Dissolved Pb concentrations remained unchanged after the application of nZVI and AMO, and the decrease of Zn leaching using AMO was controlled mainly by soil pH increase induced by its application. According to the calculated saturation indices, tripuhyite (FeSbO₄) was predicted to be the key mineral controlling Sb solubility in mine soils. Secondary Fe (hydr)oxides either originally present or newly formed due to nZVI oxidation were instrumentally identified at different stages of their transformation and metal(loid) retention. To conclude, nZVI is suitable for application to contaminated soils at a wide pH range, while the use of AMO for decreasing As leaching is limited to soils with pH ≥ 7.