Potentially Toxic Elements (PTEs) Dispersion in Alluvial Deposits from Abandoned Mining Sites

In the watersheds of abandoned mining districts, it is common to find remains of former facilities and waste dams on stream banks and slopes—a situation that results in the transport and accumulation of metal(loid)s in alluvial deposits. To analyze this problem, an area of the former mining district of Linares–La Carolina (southern Spain) was selected to evaluate the contents and distributions of Ag, As, Ba, Cu, and Pb as potentially toxic elements (PTEs) found in the mineral paragenesis. Specifically, this study focused on the Siles Stream, which runs through a sector where underground mining for the exploitation of galena veins generated abundant mining wastes, mainly waste rock and tailings. Thirty-four sediment samples from the stream bed of the Siles Stream and two sediment samples from the Guadiel River, of which it is a tributary, were analyzed. Floodplain sediments were sampled in the stream banks at the middle and lower reaches (11 samples), as well as the riverine soils developed at the mouth of the Siles Stream (22 samples). The analyzed samples presented high levels of PTEs, in most cases with values much higher than the generic reference levels established by European and regional legislation for PTEs in soils. In the case of Pb, the main metal mined in this district, contents of up to 27,074 mg·kg−1 were observed in the stream bed sediments. Very high concentrations of Pb also appeared in the floodplain sediments, with maximum values in the middle course of the stream, where the concentration reached 43,692 mg·kg−1. With respect to the sediments of the Guadiel river bed, the Pb content was 699 mg·kg−1 before the confluence with the stream and 2537 mg·kg−1 downstream, which clearly reflects the influence of the contributions from the Siles Stream. The enrichment factors (EFs) show that the sediments present a severe to very severe anthropogenic influence for Ag, As, Ba, Cu, and Pb. The geoaccumulation index (Igeo) indicates that the entire basin is extremely polluted by Pb, to which As and Ag are added in the middle course of the stream. The potential ecological risk index (RI) and pollution load index (PLI) based on the contamination factor (CF) suggested that metal loads far exceeded the reference values. Selective chemical extraction methods were used to assess the potential bioavailability of these elements in sediment and soil samples. The results showed high concentrations of Pb in the exchangeable fraction, which poses a significant ecological risk and potential human health risks.