Geochemical processes assessed by Rare Earth Elements fractionation at "Laguna Verde" acidic-sulphate crater lake (Azufral volcano, Colombia)

The geochemical behaviour of major elements, Fe, Al, Mn, and Rare Earth Elements (REE) was investigated in the “Laguna Verde” acidic crater lake of Azufral volcano (Colombia). The cold lake water (T close to 10 °C) is sulphate-dominated, due to absorption and oxidation of H2S (pH 2.1–2.7, Eh 196–260 mV), and Na-enriched (Total Dissolved Solids 0.79 g L−1). The total amount of REE dissolved in the lake ranges from 3.3 to 9.1 ppb. The REE patterns normalized to the local rocks show a Light Rare Earth Elements (LREE) depletion quite constant in the 15 samples. Similar patterns were already found in the acidic sulphate springs of Nevado del Ruiz volcano-hydrothermal system, caused by the precipitation of alunite and jarosite, absorbing LREE and hence removing them from solution. Alunite and jarosite minerals are not oversaturated at chemical-physical conditions within the lake itself, but alunite becomes oversaturated for temperatures above ≈100 °C, reigning in the underlying hydrothermal system. Water temperatures close to 75 °C were found in the northern part of the lake. Coupling the distribution of REE in lake water (LREE depleted) and the saturation indexes, we suggest that the distribution of REE in the lake water is the result of the alunite precipitation in the northern part of the lake and/or in the deeper hydrothermal system. The acidic hydrothermal fluids mobilize the REE with contents up to ≈5 orders of magnitude higher than seawater; acidic-hydrothermal systems, such as acidic crater lakes, can hence be considered potential REE “reservoirs”.