Sulphuric acid geofluid contribution on thermal carbonate coastal springs (Italy)

Hypogenic caves, developed by sulphuric acid speleogenesis, are known all over the world among which the Santa Cesarea Terme caves have been included. They are four submerged caves, located along a coastal carbonate sector in Southern Italy and hosting the outflow of coastal springs of thermal mixed waters (from 21 to 33 °C). These waters derive from the mixing of three water end members: the fresh pure groundwater of a wide karstic aquifer, the deep sulphur thermal water and the seawater. This cave system represents an almost unique case of hypogenic sea caves in carbonate environment. The thermal mixed waters have a different effect on the surrounding rocks of the caves, influencing the sulphuric acid speleogenetic process within the whole cave system. To understand the complex and overlapping natural processes acting on the development of these coastal caves, a multidisciplinary study has been carried out. This study has integrated all the data resulting from different methods and technologies, merging morphology, structural geology, hydrogeology, hydrogeochemistry and mineralogy. This multidisciplinary study has allowed to define the main geochemical processes acting within these caves, including the cave development and the formation of the mineral concretions. After the introduction of H₂S in the thermal waters, formed by the reduction of sulphates in the sedimentary deposits crossed at depth in the offshore, the oxidation occurs within the caves, producing sulphuric acid. Favoured by upwelling deep-seated thermal flows, this acid dissolves the limestone, with condensation corrosion process that involve replacement of limestone rock with gypsum. This process has resulted to be more active and remarkable within the Gattulla Cave, one of the Santa Cesarea Terme sea caves.