Abstract

The subsurface evolution of shallow-sea hydrothermal fluids is a function of many factors including fluid–mineral equilibria, phase separation, magmatic inputs, and mineral precipitation, all of which influence discharging fluid chemistry and consequently associated seafloor microbial communities. Shallow-sea vent systems, however, are understudied in this regard. In order to investigate subsurface processes in a shallow-sea hydrothermal vent, and determine how these physical and chemical parameters influence the metabolic potential of the microbial communities, three shallow-sea hydrothermal vents associated with Panarea Island (Italy) were characterized. Vent fluids, pore fluids and gases at the three sites were sampled and analyzed for major and minor elements, redox-sensitive compounds, free gas compositions, and strontium isotopes. The corresponding data were used to 1) describe the subsurface geochemical evolution of the fluids and 2) to evaluate the catabolic potential of 61 inorganic redox reactions for in situ microbial communities. Generally, the vent fluids can be hot (up to 135 °C), acidic (pH 1.9–5.7), and sulfidic (up to 2.5 mM H₂S). Three distinct types of hydrothermal fluids were identified, each with higher temperatures and lower pH, Mg and SO₄, relative to seawater. Type 1 was consistently more saline than Type 2, and both were more saline than seawater. Type 3 fluids were similar to or slightly depleted in most major ions relative to seawater. End-member calculations of conservative elements indicate that Type 1 and Type 2 fluids are derived from two different sources, most likely 1) a deeper, higher salinity reservoir and 2) a shallower, lower salinity reservoir, respectively, in a layered hydrothermal system. The deeper reservoir records some of the highest end-member Cl concentrations to date, and developed as a result of recirculation of brine fluids with long term loss of steam and volatiles due to past phase separation. No strong evidence for ongoing phase separation is observed. Type 3 fluids are suggested to be mostly influenced by degassing of volatiles and subsequently dissolution of CO₂, H₂S, and other gases into the aqueous phase. Gibbs energies (ΔG_r) of redox reactions that couple potential terminal electron acceptors (O₂, NO₃⁻, Mn^IV, Fe^III, SO₄^2 −, S⁰, CO₂) with potential electron donors (H₂, NH₄⁺, Fe^2 +, Mn^2 +, H₂S, CH₄) were evaluated at in situ temperatures and compositions for each site and by fluid type. When Gibbs energies of reaction are normalized per kilogram of hydrothermal fluid, sulfur oxidation reactions are the most exergonic, while the oxidation of Fe^2 +, NH₄⁺, CH₄, and Mn^2 + is moderately energy yielding. The energetic calculations indicate that the most robust microbial communities in the Panarea hot springs combine H₂S from deep water–rock–gas interactions with O₂ that is entrained via seawater mixing to fuel their activities, regardless of site location or fluid type.