Especiación de tierras raras en las soluciones ácidas y neutras del sistema de drenaje del Arroyo del Val (Zaragoza)

Abstract

Special geochemical characters of the Arroyo del Val drainage basin allow to study different aspects related to REE behaviour. The hydrologic system contains a main stream (Arroyo del Val) of acidic waters naturally generated (sulfate rich solutions, with high levels of Al, Fe and heavy metals, and with pH values between 3 and 4.5) and several calcium bicarbonate (sulfate) tributaries (with pH values as high as 7.5, measurable alkalinity and striking phosphate concentrations). Mixing of the acidic stream with neutral tributaries yields spectacular sulfate-iron-aluminum rich flocculants that precipitate at the confluences, along the principal stream. The concentration of REEs was measured for acidic water samples col1ected along the headwaters zone of the Arroyo del Val stream and for neutral water samples fram two tributaries. The REE content of acidic waters are enriched by 10² relative to neutral ones and the shale-normalized REE patterns for these acidic freshwaters are enriched in the inter• mediate REEs (IREE, Eu-Tb). Speciation calculations were performed on both water groups. Dominant forms of REEs in the acidic waters include free metal species (Ln³⁺ ≈ 35%) and mainly sulfate complexes ((LnSO⁺₄ ≈ 60% and minor Ln(SO₄)^-₂ ≈ 5%). REE sulfate complexation don't fractionate the REEs in solution because there is not an appreciable variation in REE sulfate complexation constants across the lanthanide serie. So, REE convex patterns in these acidic waters must be related to interaction of the acid waters with clay minerals and oxyhydroxide coatings in the paleozoic materials of drainage basin and/or with the col1oid pool of those waters. In the neutral freshwaters of tributaries dissolved REEs are complexed with carbonate and phosphate ions. REE carbonate and phosphate complexation constants across the lanthanide serie increase by several orders of magnitude from La to Lu. And so, phosphate and carbonate complexes account for 80-90 % of LREE and for 100 % of HREE. LnPO⁰₄ and Ln(PO₄)^3-₂ complexes are quite significant compared to carbonate complexes, mainly in the speciation of HREE. These results il1ustrate the importance of phosphate ion concentration and REE phosphate complexation reactions in REEs speciation calculations.