Responses of underground air and drip water geochemistry to meteorological factors: A multi-parameter approach in the Rull Cave (Spain)

Abstract

Our research aims to assess the complex interactions between the elements that constitute and influence a cave system through the analysis of an extensive dataset of climatic and environmental parameters (222Rn, CO2, drip rates, chemical composition, and environmental isotopes) measured in air, water, and solid in the Rull Cave (southeastern Spain). Of particular importance is understanding the effect of rainfall and temperature on water and gas transport through the epikarst and the involved processes. Our results show that the cave gaseous concentration patterns do not only depend on the temperature-caused movement of air masses, but they can also be affected by abundant rainfall. The δ18O and δD composition of cave water also relies on such precipitations for the effective transfer of the rainfall signal into the cave, which can take between 3 and 7 days. The elemental ratios (Sr/Ca and Mg/Ca) show high responsiveness to the water drip rate, hinting that enhanced prior calcite precipitation (PCP) occurs at slower drip rates. Despite this, and regardless of drip rates, calcite saturation indices follow a seasonal variation pattern inversely proportional to the cave air CO2 concentration, while δ13C-DIC is proportional. Our results show how the interlinkage between these multiple components defines the dynamics of the atmosphere-soil-cave system. Cave monitoring is then essential to understand the karstic vadose zone, which is highly sensitive to climatic influence and its changes.