Geochemical behaviour and transport of technology critical metals (TCMs) by the Tinto River (SW Spain) to the Atlantic Ocean

Highlights: • Acidity boosts the dissolution of technology critical metals in Tinto River. • Particulate REE, Y and Sc are also transported by Al-silicates and Al-sulphates. • Tl concentration controlled by coprecipitation/sorption in Fe minerals and diatoms. • The Tinto River releases 0.01%–0.09% of dissolved global fluxes of REE, Y and Ga. This paper addresses the behaviour of several technology critical metals (TCMs), i.e., rare earth elements (REEs), Y, Sc, Ga and Tl, in the Tinto River (SW Spain), quantifying their fluxes to the Atlantic Ocean and unravelling the governing geochemical processes controlling their solubility. To accomplish this goal, a high-resolution (2–24 h) sampling was performed during the hydrological year 2017/18. Mean dissolved concentrations of 380 μg/L of REE, 99 μg/L of Y, 15 μg/L of Sc, 9.2 μg/L of Ga and 4.8 μg/L of Tl were found. Most TCMs followed a behaviour similar to that of sulphate and base metals throughout the year, exhibiting a quasi-conservative behaviour due to acidic conditions. However, dissolved Tl concentrations seem to be strongly controlled by Tl incorporation onto secondary minerals and diatoms deposited on the riverbed, especially during the dry season. The remobilization of riverbed sediments led to the transport of significant amounts of TCMs associated with particulate matter, especially Al oxy-hydroxy-sulphates or Al-silicates rather than Fe precipitates (except for Tl and Ga). Around 5.8 t of REE, 1.3 t of Y, 248 kg of Sc, 139 kg of Ga and 138 kg of Tl were delivered annually in their dissolved forms by the Tinto River to the Atlantic Ocean, which constitutes around 0.09% of the dissolved global flux into the oceans of Y, 0.02% of the REE flux, 0.01% of the Ga flux and 0.001% of the Sc flux.