Ioiô Cave is a 4.7 km long maze cave in the southern tip of the Irecê Basin (Bahìa, Brazil), and although still actively forming today, it hosts signs of a long speleogenetic history. Deep rising hydrothermal fluids weathered the carbonates, creating dark ghost-rocks and quartz and dolomite veins, mainly in the anticlinal hinges and below the siliciclastic seals. This silicification, although not directly dated, is probably associated with the end of the Brasiliano-age tectono-thermal activity (Lower Cambrian) based on isotopic and trace element data and regional tectonic correlations. Since the Plio-Quaternary, the progressive exhumation of the carbonate reservoir increasingly favored the introduction of meteoric oxygen-rich water from the surface, causing sulfide oxidation at shallow aquifer depth. The CO₂ produced by Sulfuric Acid Speleogenesis (SAS) rose along fractures and degassed at shallow depth, producing carbonic speleogenesis close to the water table. This carbonic speleogenesis, probably still active, produced a maze network, by horizontal diffusion of aggressive fluids from the feeders. Surface breaching increased air flow activating degassing and supersaturation of the basins, with deposition of subaqueous calcite shelves, carved with bubble trails resulting from CO₂ degassing related to still-ongoing pyrite oxidation (localized SAS).

Fractured and karstified carbonate units are key exploration targets for the hydrocarbon industry as they represent important reservoirs. Furthermore, large water reserves and geothermal systems are hosted in carbonate aquifers. This paper documents the relationships between stratigraphy, structural patterns, silicification, and the spatial-morphological organization of a 3D multistorey cave system developed in a Neoproterozoic mixed carbonate-siliciclastic sequence. We found that the combination of lithology, silicification, fracture patterns (controlled by lithostratigraphic variability), and petrophysical properties control the formation of high or low permeability zones; their distribution was fundamental for the spatial organization of dissolution and the compartmentalization of the resulting conduit system in different speleogenetic storeys. We propose a deep-seated hydrothermal origin for the fluids involved in the main phases of karst formation. Warm and alkaline hydrothermal fluids caused silica dissolution, followed by chalcedony and quartz reprecipitation in pore space and fractures. Rising fluids concentrated along through-going vertical fracture zones in the lower storey, whereas sub-horizontal bedding-parallel fluid flow was focused on sedimentary packages containing highly silicified dolostones (SiO₂>80 wt%) characterized by high permeability. The Calixto Cave is an enlightening example for the complex speleogenetic history affecting a mixed carbonate-siliciclastic succession where the combined effect of silicification and hydrothermal karst dissolution can potentially generate high-quality reservoirs.

Caves developed in carbonate units have a significant role in fluid flow, but most of these subsurface voids are below seismic resolution. We concentrated our study on four caves to determine the roles of fractures and folds in the development of karst conduits that may form flow pathways in carbonate reservoirs. We performed structural field investigations, petrographic analyses, and geometric characterization using Light Detection and Ranging (LIDAR) for caves in Neoproterozoic carbonates of the Salitre Formation, central part of the São Francisco Craton, Brazil. We found that the conduit shape, usually with an ellipsoidal cross-section, reflects the tectonic features and textural variations. Carbonate layers containing pyrite and low detritic mineral contents are generally karstified and appear to act as favorable flow pathways. Our results indicate that the development of the karst system is related to fracture corridors formed along parallel and orthogonal sets of fold hinges, which provide preferential pathways for fluid flow and contribute to the development of super-K zones. This study provides insights into the prediction of subseismic-scale voids in carbonate reservoirs, with direct application for the hydrocarbon and hydrogeology flow and storage.