Calderas are depressions formed by some of the largest volcanic eruptions. Their long-lived inter-eruptive periods are occasionally interrupted by phases of unrest, in which escalating seismicity, ground deformation and gas emissions raise concerns of potential volcano reawakening. However, interpretation of such physico-chemical signals is complicated by few examples of monitored unrest that culminated into eruption and by our fragmentary understanding of the drivers and timescales of caldera reactivation. Here we show that multi-decadal gas observations at the restless Campi Flegrei caldera in Italy record an unprecedented increase in isotopically light sulfur release from fumaroles since 2018. We then use hydrothermal gas equilibria and numerical simulations of magmatic degassing to propose that such a change in sulfur emissions results from decompression-driven degassing of mafic magma at ≥6 km depth, along with some extent of sulfur remobilization from hydrothermal minerals. Examination of a global dataset indicates that, despite the diversity in eruptive behaviour and tectonic setting, increasing sulfur output may be a common process during unrest escalation at calderas generally. Hence, our observations and models of sulfur behaviour may inform interpretations of unrest and hazard assessment at reawakening calderas and hydrothermal active volcanoes worldwide.

We present a new geometrical method capable of quantifying and illustrating the outcomes of a three‐component mixing dynamics. In a three‐component mixing scenario, classical algebraic equations and endmember mixing analysis (EMMA) can be used to quantify the contributions from each fraction. Three‐component mixing of natural waters, either in an element–element plot or by using the EMMA mixing subspace is described by a triangular shaped distribution of sample points where each endmember is placed on an apex, while each side corresponds to the mixing function of the two endmembers placed at the apex, considering the third endmembers' contribution equal to zero. Along each side, the theoretical mixing fractions can be computed using mass balance equations. Samples with contributions from three endmembers will plot inside the triangle, while the homogeneous barycentric coordinate projections can be projected onto the three sides. The geochemistry observed in the mineralized Ferrarelle aquifer system (southern Italy) results from three‐component mixing of groundwater, each with diagnostic geochemical compositions. The defined boundary conditions allow us to parameterize and validate the procedures for modelling mixing, including selection of suitable geochemical tracers.

The Riardo basin hosts groundwater exploited for the production of high quality, naturally sparkling, bottled water (e.g., Ferrarelle water), and circulating in a system constituted by highly fractured Mesozoic carbonates, overlain by more impervious volcanic rocks of the Roccamonfina complex. The two formations are locally in hydraulic connection and dislocated by deep-rooted faults. The study aimed at elucidating groundwater origin and circulation, using isotopic tracers (δ¹⁸O, δ²H, δ¹¹B and ⁸⁷Sr/⁸⁶Sr) coupled to groundwater dating (Tritium, CFCs and SF₆). Besides recharge by local precipitation over the Riardo hydrogeological basin, stable isotope ratios in water indicated an extra-basin recharge, likely from the elevated surrounding carbonate reliefs (e.g., Maggiore and Matese Mts.). The mineralization process, promoted by the deep CO₂ flux, controls the B and Sr contents. However, their isotopic ratios did not allow discriminating between circulation in the volcanic and in the carbonate aquifers, as in the latter the isotopic composition differed from the original marine signature. Groundwater model ages ranged from ~ 30 years for the volcanic endmember to > 70 years for the deep, mineralized end-member, with longer circuits recharged at higher elevations. Overall, the results of this study were particularly relevant for mineral water exploitation. A recharge from outside the hydrogeological basin could be evidenced, especially for the more mineralized and valuable groundwater, and an active recent recharge was detected for the whole Riardo system. Both findings will contribute to the refinement of the hydrogeological model and water budget, and to a sustainable development of the resource.

A theoretical pattern for Fe and As co-precipitation was tested directly in a groundwater natural system. Several monitoring wells were sampled to identify the different endmembers that govern the hydrodynamics of the Ferrarelle Groundwater System in the Riardo Plain (Southern Italy). In agreement with recent investigations, we found a mix of a deep and a shallow component in different proportions, resulting in a specific chemical composition of groundwater in each well depending on the percentages of each component. The shallow component was characterized by EC ~ 430 µS/cm, Eh ~ 300 mV, Fe ~ 0.06 µmol/L and As ~ 0.01–0.12 µmol/L, while the deep component was characterized by EC ~ 3400 µS/cm, Eh ~ 170 mV, Fe ~ 140 µmol/L and As ~ 0.59 µmol/L. A general attenuation of As and Fe concentration that was not due to a simple dilution effect was observed in the mixing process. The oxidation of Fe(II) to Fe(III) produces solid precipitates which adsorb As from solution and then co-precipitate. The reactions pattern of Fe(II) oxidation and As adsorption gave a linear function between [As] and [Fe], where the angular coefficient depends on the [O₂]/[H⁺] ratio. Chemical data obtained from our samples showed a very good agreement with this theoretical relationship. The investigated geochemical dynamics represented a natural process of attenuation of Fe and As, two undesirable elements that usually affect groundwater quality in volcanic aquifers in central-southern Italy, which are exploited to supply drinking water. Graphic abstract