Hydrogeochemistry of trace and rare earth elements in the Caviahue-Copahue Volcanic Complex

The Caviahue-Copahue Volcanic Complex is one of the most studied active volcanic systems in the South American Andean range, and yet little research has focused on trace and rare-earth elements of waters, especially during an eruptive cycle. In this study, we sampled and investigated natural waters from 23 sites (involving the crater lake, hot springs, streams, rivers, and bubbling pools) in two campaigns in 2017 and 2018, using physicochemical parameters, major, trace and rare-earth elements concentrations. With this novel dataset, it was possible to identify, characterize and compare three groups of waters with distinctive hydrofacies. Indeed, the normalization of water compositions against host rock concentrations showed a particular trace element pattern for each group of waters. Although the absolute concentrations of the elements in each sampling site changed from 2017 to 2018, the normalized patterns did not. Boron, As, Cd, Tl, Se, and Te, commonly recognized as volatile, are the main trace elements that magmatic gases supply to the system headwaters, whereas elements such as Ca, K, and Ba are affected by precipitation of secondary minerals (gypsum, anhydrite, barite, jarosite, and alunite). Furthermore, the main river draining the summit volcano shows a steep decrease in As, Cr, and V concentrations correlated to the precipitation of Fe and Al hydroxysulfates (schwertmannite and basaluminite, respectively). Moreover, it is the first time that a comparison between the different water groups is made using the patterns of the rare-earth elements, allowing us to identify and separate depletion patterns due to dilution processes from those due to precipitation processes.