Spatio-temporal variations of cave-air CO2 concentrations in two Croatian show caves: Natural vs. anthropogenic controls

Carbon dioxide (CO2) concentration (CDC) plays an important role in karst processes, governing both carbonate deposition and dissolution, affecting not only natural processes, but also human activities in caves adapted for tourism. Its variations due to various controlling parameters was observed from 2017 to 2021 in two Croatian show caves (Manita peć and Modrič) where we examined inter- and within-cave correlation of internal aerology regarding the sources, sinks and transport mechanism of CDC in a karst conduit setting. In both caves, the main sources of CO2 are: i) plant and microbial activity i.e. root respiration and organic matter decay within soil horizons and fractured epikarst, and ii) degassing from CO2-rich percolation water. The main sink of CO2 is dilution with outside air due to cave ventilation. Chimney-effect driven ventilation controlled by seasonal differences between surface and cave air temperatures shows winter (ToutTcave ) ventilation regime, which are modulated by the geometry of cave passages, the transmissivity of the overlying epikarst, and occasionally by the external winds, especially the gusty north-eastern bora wind. In these terms, the Modrič Cave appears to be more confined and less ventilated, with a substantial CDC difference between the left (550-7200 ppm) and right (1475- >10,000 ppm) passages. The Manita peć Cave is, in contrast, ventilated almost year-round, having 7 months of CDC equilibrated with the outside atmosphere and the highest summer CDC values of ~1410 ppm. In both caves, at the current level of tourist use, anthropogenic CO2 flux is not a matter of concern for cave conservation. In turn, in the innermost part of the right Modrič Cave passage visitors’ health might be compromised, but the tourists are allowed only in the left passage. Speleothem growth rate, recognized as a useful palaeoenvironmental proxy for speleothem-based palaeoclimate studies, strongly depends on CDC variations, so the high CDCs recorded in the Modrič Cave indicate the potential periods with no speleothem deposition due to the hampered degassing of CO2 from the dripping groundwater. The opposite effect i.e. enhanced ventilation (that supports calcite precipitation) during the windy glacials/stadials, as well as substantial vegetational changes must also be taken into consideration when interpreting environmental records from spelean calcite