Geochemical behaviour of rare earth elements (REE) along a river reach receiving inputs of acid mine drainage

Total and dissolved rare earth elements (REE) were studied in a river reach affected by several inputs of acid mine drainage. The first four acidic discharges were of lesser importance compared to the last (Agrio River, coming from the Río Tinto mines), which transported high loads of Fe and Al (2.1 and 4.2 ton/day, respectively) together with REE (16.4 kg/day) and other trace elements. In the acid mine drainage (AMD) sources, practically all the REE were dissolved and the North American Shale Composite (NASC)-normalized patterns showed an enrichment in medium REE, although some differences exist between the patterns of each source. The pH values in the river reach upstream of the confluence with the Agrio River ranged between 8.01 and 7.03, and most of the Fe and Al from the AMD sources precipitated. Downstream of this acidic discharge, the pH decreased to 2.98. Upstream of the first AMD input, the dissolved and total concentrations of ΣREE were very low (<0.6 μg/L). In the river reach affected by AMD that maintains pH values >7, concentrations of ΣREE increased (up to 25 μg/L), mainly transported by the particulate phase. In the reach downstream of the Agrio River with acidic conditions, REE behaved conservatively. The REE NASC-normalized patterns of the river samples resemble that of the AMD sources, although an enrichment of heavy REE in the dissolved phase is observed linked to complexation by carbonates. Cerium and particularly La also show higher dissolved percentages, similar to HREE, which must be due to the lower affinity of these elements to be sorbed onto Fe oxyhydroxides. Variations in Ce and Eu anomalies are observed along the river reach as a consequence of the different AMD inputs. However, the values of the Ce anomaly are higher in total samples than in dissolved samples. Speciation results indicate that these differences are not caused by differences in oxidation states but by slight differences in the hydrogeochemical behaviour of Ce with respect to La and Nd.