Hydrogeochemical Characterization of Volcanic Lakes at the Sete Cidades Volcano (São Miguel, Azores)

The hydrogeochemical characterization of shallow volcanic lakes at the Sete Cidades Volcano (São Miguel, Azores) provides new insights into the processes controlling water chemistry in low-depth lacustrine systems within active volcanic environments. Fourteen lakes (0.6–4 m deep) were sampled during two campaigns (winter 2024 and spring/summer 2025), combining in situ physicochemical measurements and major ion analyses along vertical profiles. The lakes are holomictic, cold (11.3–17.6 °C), slightly acidic (pH 5.66–5.95), and weakly mineralized (EC ~65–69 µS/cm), indicating dilute waters of predominantly meteoric origin. Hydrochemical facies are dominated by Na–Cl type, with strong correlations between chloride and conductivity (r = 0.857), supporting a major contribution from marine atmospheric deposition. To move beyond correlation-based interpretation, Gibbs diagrams and saturation indices (PHREEQC) were applied to constrain the dominant geochemical processes. Most samples plot within the precipitation dominance field, while all calculated saturation indices are negative (SI < 0), indicating undersaturation with respect to carbonate, evaporite, and silicate minerals. These results demonstrate that water chemistry is primarily controlled by atmospheric inputs, with only minor contributions from water–rock interaction and negligible influence of evaporation or mineral equilibrium processes. Seasonal increases in HCO3− and dissolved CO2 at depth suggest enhanced organic matter decomposition during warmer periods, highlighting the role of biogeochemical processes in modulating carbon dynamics in shallow systems. The absence of a clear hydrothermal signature further distinguishes these lakes from deeper volcanic systems in the Azores. This study provides the first integrated hydrogeochemical framework for shallow volcanic lakes in the region, combining classical hydrochemistry with process-based tools. The results establish a quantitative baseline for assessing environmental change and improve the interpretation of external (atmospheric) versus internal (geochemical and biological) controls in volcanic lake systems.