Tracking geochemical signatures of rare earth and trace elements in spring waters and outcropping rocks from the hidden geothermal system of Acoculco, Puebla (Mexico)

Abstract

A geochemical mapping of rare earth (REE) and other trace elements in water and rock samples of the hidden geothermal system of the Acoculco caldera was carried out. REE and other trace elements were measured at low concentrations in waters (ΣREE <50 μg/L) and rocks (ΣREE <773 μg/g), and used, for the first time, to understand the water-rock interaction processes of this geothermal system. A bimodal frequency distribution of pH was found among acidic waters (pH <3.5) that emerge from cold springs located inside the caldera, and slightly-acid to hot alkaline spring waters (pH 5 to 9.2) from outside the caldera. The geochemical modelling of REE showed that minerals containing Al3+, Fe, and F− were the main phases that control their concentrations in acidic waters. Different degrees of REE complexation in waters located inside the Acoculco caldera (Alcaparrosa and Los Azufres) clearly showed new signatures of geothermal activity. LnSO4+ complexes and free ions of Ln3+ were identified as major species of the acidic waters of Alcaparrosa, whereas in less acidic waters of Los Azufres, LnF2+ show an increase in their complexation percentages. The REE chondrite-normalized patterns observed in acid waters display a depletion from light-REE (LREE) to heavy-REE (HREE), and an inverse correlation between high REE concentrations and acid pH's. The REE concentration in felsic and intermediate rocks shows “gull-wing” chondrite-normalized patterns characterised by an enrichment of LREE, a negative anomaly of Eu, and depletion of HREE with a flat tendency. The present study of water-rock interaction contributed to the identification of new geochemical signatures of major and trace elements that provide new evidences of deep formation temperatures between 200 °C and 300 °C, becoming in an effective tool for finding out convincing anomalies in hidden geothermal systems.