RESUMO
For the last forty-five years (from 1974 to present) ferroalloy production in Bagnolo Mella, Northern Italy, has generated particulate emissions enriched in potentially toxic metals and metalloids including arsenic (As), lead (Pb) and manganese (Mn). Of these, Mn is unique in that it has a significant background concentration and is seldom studied as a contaminant but is potentially a significant toxin derived from dusts regionally. Here we examine the distribution, redistribution, speciation and bioavailability of the Mn-contaminated top soils affected by atmospheric emissions adjacent to the ferroalloy plant. Four sites, variably located in the study area in terms of both distance and direction from the plant, were considered as representative of increasing levels of industrial influence. Soil profiles showed that metal concentrations (measured by X-ray fluorescence) varied considerably by location, i.e. higher in the sites closer to the plant and also at the surface level, although distributed throughout the top 15 cm, suggesting appreciable redistribution possibly due to soil mixing or infiltration. Most metal concentrations were correlated, except Mn which was independent and more variable across the sites than the other elements. Sequential chemical extractions indicated that Pb was primarily associated with Mn oxides, while As was most significantly associated with iron oxides. When Mn concentration significantly exceeded background levels, it was present in phases that were resistant to acid dissolution, very different from typical uncontaminated soils. X-ray Absorption Near Edge Spectroscopy (XANES) analyses suggested this recalcitrant Mn phase is likely a Mn-bearing spinel such as magnetite, that can be particularly toxic if ingested or inhaled. These first results highlight the legacy of ferroalloy production on surrounding soils, as well as the importance of Mn speciation for soil apportionment evaluation and human exposure estimation.