Early hypogenic carbonic acid speleogenesis in unconfined limestone aquifers by upwelling deep-seated waters with high CO<sub>2</sub> concentration: a modelling approach

Abstract

Abstract. Here we present results of digital modelling of a specific setting of hypogenic carbonic acid speleogenesis (CAS). We study an unconfined aquifer where meteoric water seeps through the vadose zone and becomes saturated with respect to calcite when it arrives at the water table. From below, deep-seated water with high pCO2 and saturated with respect to calcite invades the limestone formation by forced flow. Two flow domains arise that host exclusively water from the meteoric or deep-seated source. They are separated by a water divide. There by dispersion of flow, a fringe of mixing arises and widening of the fractures is caused by mixing corrosion (MC). The evolution of the cave system is determined by its early state. At sites with high rates of fracture widening, regions of higher hydraulic conductivity are created. They attract flow and support one-by-one mixing with maximal dissolution rates. Therefore, the early evolution is determined by karstification originating close to the input of the upwelling water and at the output at a seepage face. In between these regions, a wide fringe of moderate dissolution is present. In the later stage of evolution, this region is divided by constrictions that originate from statistical variations of fracture aperture widths that favour high dissolution rates and focus flow into this region. This MC-fringe instability is an intrinsic property of cave evolution and is present in all scenarios studied. We have investigated the influence of defined regions with higher fracture aperture widths. These determine the cave patterns and suppress MC-fringe instabilities. We have discussed the influence of the ratio of upwelling water flux rates on the rates of meteoric water. This ratio specifies the position of the mixing fringe and consequently that of the cave system. In a further step, we have explored the influence of time-dependent meteoric recharge. Furthermore, we have modelled scenarios where waters are undersaturated with respect to calcite. These findings give important insight into mechanisms of CAS in a special setting of unconfined aquifers. They also have implications for the understanding of corresponding sulfuric acid speleogenesis (SAS).

Combined use of conventional and clumped carbonate stable isotopes to identify hydrothermal isotopic alteration in cave walls

“…While the water composition is clearly a mixture of two components, the positive correlation in δ 18 O cc − δ 13 C cc space cannot be explained by calcite precipitation due to mixing of two fluids. First, the two fluids will need to be highly saturated in calcite, as mixing of two fluids saturated in calcite at different equilibrium concentrations of Ca 2+ produces a mixture with lower calcite saturation due to the curvature of the calcite equilibrium line, that will lead to calcite dissolution (i.e., mixing corrosion) 70 – 72 . Second, the very small change observed in the δ 13 C cc values would require two fluids of such contrasting origin, such as meteoric and deep-seated, to have similar carbon isotopic composition, which is highly unlikely.…”