Groundwater geochemistry observations in littoral caves of Mallorca (western Mediterranean): implications for deposition of phreatic overgrowths on speleothems

Phreatic overgrowths on speleothems (POS) precipitate at the air-water interface in the littoral caves of Mallorca, Spain. Mainly composed of calcite, aragonite POS are also observed in specific locations. To characterize the geochemical environment of the brackish upper water column, water samples and salinity values were collected from water profiles (0-2.9 m) in April 2012 and March 2013 near aragonite POS in Cova des Pas de Vallgornera and calcite POS in Coves del Drac (hereafter, Vallgornera and Drac). Degassing of CO2 from the water was evidenced by the existence of lower dissolved inorganic carbon (DIC) concentration and enriched δ13CDIC values in a thin surface layer (the uppermost 0.4 m), which was observed in both profiles from Drac. This process is facilitated by the efficient exchange of cave air with the atmosphere, creating a CO2 partial pressure (pCO2) disparity between the cave water and air, resulting in the precipitation of calcite POS as CO2 degasses from the water. The degassed upper layer was not observed in either profile from Vallgornera, suggesting that less efficient cave ventilation restricts outgassing of CO2, which also results in accumulation of CO2 in the cave atmosphere. The presence of an existing uncorroded POS horizon, as well as higher concentrations and large amplitude fluctuations of cave air pCO2, may indicate that aragonite POS deposition is currently episodic in Vallgornera. Ion concentration data from monthly water samples collected in each cave between October 2012 and March 2013 indicate higher Mg:Ca, Sr:Ca, Ba:Ca and Sr:Mg ratios in Vallgornera. Salinity alone does not appear to be a viable proxy for ions that may promote aragonite precipitation or inhibit calcite precipitation. Instead, these ions may be contributed by more intense bedrock weathering or deep groundwater flow