The use of rare earth element profiles as a proxy for a fractionation source and mine-waste provenance

Rare earth elements (REEs) have been determined in acid mine drainage samples from the Wiśniówka area, south-central Poland. Two benchmark acid pit ponds, i.e., Podwiśniówka (PwIIb) and Wiśniówka Duża (WD), have shown diverse contents of sulfates, phosphates, REEs and metal(loid)s. Moreover, these ponds exhibit different NASC-normalized REE concentration patterns: (i) a positive middle REE anomaly in PwIIb and (ii) a positive heavy REE anomaly in WD, regardless of sampling time. This MREE anomaly has also been highlighted in a small tailings pile pool showing high contents of metal(loid)s, including As (3.86 g/L) and REEs (90.1 mg/L). In contrast, the light REE (LaEu)-rich profiles are recorded in all Upper Cambrian rock series of the study area. However, the Pw geologic section is distinctly enriched in pyrite, goethite/hematite and carbonaceous clayey-silty shales compared to its WD counterpart that contains a lesser amount of these components, but many more quartzite/sandstone beds. The Pw mineral-lithologic pattern favors selective partitioning of heavy REEs to abundant Fe- and Al-oxyhydroxides and organic matter. Both very short solute transport from sheer rock faces to pit ponds and a low pH of acid waters (mean of 2.3 to 3.0) indicate that scavenging/adsorption and mineral co-precipitation of REEs in a water column may be negligible. This inference is also backed up by overlapping REE profiles at different depths of acid pit ponds. Taken together, this implies that preferential fractionation of REEs takes place primarily during on-site weathering of pyrite and REE-bearing minerals in different rock media thus leading to changes in the Pw- and WD shale-normalized REE concentration patterns at source. The characteristic Pw roof-shaped (convex-up) profile in water samples has been used as a proxy for tracing the most detrimental Podwiśniówka As-bearing mine-waste that were scattered within the mining area a couple of years ago.