Stable isotope and anthropogenic tracer signature of waters in an Andean geothermal system

In the present study, we combined stable isotopes and anthropogenic tracers to investigate the origin, residence times, and evolution of thermal waters in the Lonquimay-Tolhuaca Volcanic Complex (LTVC) of the southern Chilean Andes. A total of 20 water samples from springs discharging at a broad range of temperatures (8–96 °C) were collected and analyzed for major ion geochemistry, stable isotope ratios (δ²H, δ¹⁸O, δ¹³CTDIC), dissolved chlorofluorocarbons (CFCs) and sulfur hexafluoride (SF₆). In addition, we compiled all available data on the isotopic composition of precipitation in the region to derive the local meteoric water line. Coupled with a Rayleigh-fractionation model of precipitation, we provide constraints on the elevation at which infiltration and recharge to the system is produced. δ¹³CTDIC values are consistent with the bulk of dissolved inorganic carbon being derived from the addition of soil CO₂ to an atmospheric source, while magma degassing and boiling processes are evidenced in samples discharging directly on the flanks of volcanoes. The isotopic composition of thermal water, once heated at depth, is further modified by CO₂ degassing and carbonate precipitation during ascent. All geothermal samples contain low but detectable concentrations of CFC-11, CFC-12, CFC-113, and SF₆, suggesting the addition of only a small fraction (2–22%) of modern meteoric water. The discharge temperature of naturally outflowing springs in the LTVC correlates directly with the age distribution of the water samples. This difference in residence times is attributed to the distinct subsurface circulation pathways of each water type—i.e., the shallow, diffuse flow of cold groundwater vs. the deep, focused circulation of thermal water along fault zones. Conduit flow along high vertical permeability networks allows hydrothermal fluid to remain relatively unmixed with shallow meteoric water during ascent. Data from this study confirm that fault-fracture meshes with different orientations exert a first order control on the residence times, ascent, and mixing rates of thermal waters in this segment of the Andean Cordillera, thus modulating their chemical and isotopic signature. Additionally, our results show that the combined use of conventional hydrogeochemical and isotopic data with environmental tracers, including anthropogenic CFCs and SF₆, is a powerful tool to better understand the dynamics of geothermal systems.