Rare earth elements and yttrium in cold mineral and thermal (~30-60 °C) waters from Tertiary aquifers in the Mura Basin, north-eastern Slovenia: A review

Abstract

Cold mineral and thermal waters from Tertiary aquifers in the Mura Basin mainly belong to the Ca-(Mg)-(Na)-HCO₃ and Na-HCO₃ hydrogeochemical facies, respectively, and the concentrations of yttrium (Y) and lanthanides or rare earth elements (REEs) are far below (10^-2 – 10^-4) the abundances in the aquifer sediments. Mineral waters are high pCO₂, and the plots of concentrations of YREEs normalised to Post Archean Australian Shale (PAAS) show fractionation of Y and heavy REEs (HREEs) over light REEs (LREEs), and a significant positive europium (Eu) anomaly. Thermal water from regionally developed aquifer Thermal I (recently also termed the Mura/Ujfalu Formation aquifer) shows a similar PAAS-normalised pattern with an obvious positive Eu anomaly and the tendency of enrichment with middle REEs (MREEs). The plots of PAAS-normalised YREE concentrations in thermal waters from the underlying low-permeability aquifers with poorly developed fracture porosity and abundant CO₂ are flat with insignificant positive Eu anomaly. The abundance and fractionation of YREEs in mineral and thermal waters seems to be mainly controlled by the presence of carbonate complexing ligands, permeability of the aquifers and the related time of water-rock interaction.
YREEs have been used for geochemical recognition of overexploitation of the Sob-1 well that yields mixed waters from Thermal I and the underlying low-permeability aquifers. The well overexploitation has resulted in continuous 30-to-80-minute changes in hydrodynamic pressure in Thermal I, and the related change in temperature and chemical composition of abstracted water. Leakage from clayey-silty layers rich in coal and organic matter has been recognised over a several-year time scale by increased abundances of total organic carbon (TOC), YREEs, gallium (Ga), thallium (Tl) and selenium (Se). PAAS-normalised plots of YREE concentrations have shown significant positive anomalies of samarium (Sm), terbium (Tb) and holmium (Ho) and indicate the YHREE complexing ligands could be, beside carbonate species, humic and/or fulvic acids.