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

  • L. E. ZuffianòEmail author
  • M. Polemio
  • R. Laviano
  • G. De Giorgio
  • M. Pallara
  • P. P. Limoni
  • F. Santaloia
Original Article


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.


Sulphuric acid speleogenesis Carbonate aquifer Thermal springs Coastal aquifer Italy 



The present activity has been performed in the frame of the VIGOR Project, aimed at assessing the geothermal potential and exploring geothermal resources of four regions in southern Italy. VIGOR is part of the activities of the Interregional Programme “Renewable Energies and Energy Savings FESR 2007–2013–Axes I Activity line 1.4 ‘Experimental Actions in Geothermal Energy’. The authors acknowledge the management of VIGOR Project, and in particular: Dr. Piezzo of MiSE-DGENRE (Directorate General for Nuclear Energy, Renewable Energy and Energy Efficiency of the Ministry for Economic Development); Dr. Brugnoli, Director of CNR-DTA (National Research Council of Italy, Department of Sciences of the Earth System and Environmental Technologies); the coordinator, Drs. Manzella from CNR-IGG. Thanks are also due to the whole staff of the Santa Cesarea Terme spa for the availability displayed during the research activities performed for the pilot site of the study. We thank to Mr. Nicola Mongelli and Mrs Rossana Vittoria to their technical support for the SEM-EDS and XRPD analyses. SEM-EDS and XRPD analyses were performed with, respectively, SSD and X’Celerator detectors of “Laboratorio per lo Sviluppo Integrato delle Scienze e delle TEcnologie dei Materiali Avanzati e per dispositivi innovativi (SISTEMA)” of the University of Bari.

Compliance with ethical standards

Conflict of interest

The authors of the paper “Sulphuric acid geofluid contribution on thermal carbonate coastal springs (Italy)” declares that there is no conflict of interest regarding the publication of this paper.


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • L. E. Zuffianò
    • 1
    Email author
  • M. Polemio
    • 1
  • R. Laviano
    • 2
    • 3
  • G. De Giorgio
    • 1
  • M. Pallara
    • 2
    • 3
  • P. P. Limoni
    • 1
  • F. Santaloia
    • 1
  1. 1.CNR-IRPI, National Research Council-Research Institute for Geo-Hydrological ProtectionBariItaly
  2. 2.Centro Interdipartimentale Laboratorio di Ricerca per la Diagnostica dei Beni CulturaliUniversità degli Studi di Bari Aldo MoroBariItaly
  3. 3.Dipartimento di Scienze della Terra e GeoambientaliUniversità degli Studi di Bari Aldo MoroBariItaly

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