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.

The world produces 1.7 × 10⁸ metric tons of gravel and sand per year (USGS, 2015) creating many gravel pit lakes that change the morphology and drainage pattern of catchments. Gravel pit lakes abruptly intersect the geologic layering creating an environment where surface and groundwater will interact and where elaborate food webs can develop. Here we preview previous work on gravel pit lakes and compiled a comprehensive hydrochemical database to compare the chemistry of gravel pit lake water with other types of surface and groundwater. Water budget calculations confirm that gravel pit lakes cause freshwater loss in temperate and Mediterranean climates where surface water evaporation is larger than the actual evapotranspiration of vegetated land that was replaced by the gravel pit lakes. Groundwater fed gravel pit lakes where evaporated water is replaced by groundwater are especially sensitive to climate change.The gravel pit lakes included in this review have a relatively low acidity and high alkalinity most likely caused by weathering and leaching of carbonates in the catchment. The inflow of groundwater is a key process in gravel pit lakes with important consequences. The creation or presence of the gravel pit lakes may induce fluctuation of the up-stream water table which enhances groundwater flow and redox reactions in the soil. Groundwater rich in dissolved elements typically meets more alkaline water in gravel pit lakes enhancing the precipitation of metal oxides, calcite and other composite minerals including phosphorus (P), calcium (Ca) and carbon (C). Gravel pit lakes provide many different ecological habitats increasing the biodiversity in typically an agricultural or urban setting. Plant and animal species observed in gravel pit lakes consists of phytoplankton, zooplankton, micro plankton, macrophytes, fish and birds similar to natural lakes but the fact that gravel pit lakes may be only groundwater fed, or instead in open contact with rivers causes large variations between the ecosystem of different lakes. Plants and animal species take part in the chemical cycling of gravel pit lakes by, among others, uptake of atmospheric carbon dioxide (CO₂) and nitrogen (N₂), of dissolved compounds including bicarbonate (HCO₃), iron (Fe) and manganese (Mn); of elements including phosphate (P) and Fe from lake sediments, and carbon mineralization and burial. Gravel pit lakes may contribute to denitrification of groundwater as N is consumed by plankton, but they may also enhance the mobilization of soil-bound compounds like potentially toxic (trace) metals released from aquifer sediments. The creation of gravel pit lakes provides more available sites for carbon burial but once deposited on the lake bottom, metals and other elements may be released again due to redox cycling, influenced by climatic or land use change. Gravel pit lakes are water bodies of recent formation and so far only a few different settings have been studied in detail compared to other types of natural- and man-made lakes. From this review it is evident that gravel pit lakes are hydrochemically most similar to so called 'marl lakes' or 'nutrient rich' lakes. Key areas for further research include the study of gravel pit lakes in other settings to better separate the similarities and differences between natural and gravel pit lakes. Also the feedback mechanisms between change in land use and climate, ground- and lake water chemistry ecological functioning and use of the gravel pit lakes need to be addressed.

Flow-through brackish gravel pit lakes near the Adriatic Coast of Emilia Romagna (Italy) in the Mediterranean have a large influence on the hydrologic budget of the watershed. Strong evaporation in combination with intense drainage of the low lying basins enhances groundwater inflow into the lake. Precipitation falling on the lakes is mixed with brackish/saline lake water causing the loss of freshwater. The gravel pit lakes are characterized by a high salinity (TDS = 4.6-12.3 g L"1) and high pH (8.5). Stable isotope data show that gravel pit lake water is fed by groundwater which is a mix of Apennine River water and (Holocene) Adriatic Seawater, subsequently enriched by evaporation. The slope of the local evaporation line is 5.4. Conservative tracer and water budget modeling shows that the final Cl concentration depends strongly on the ratio of evaporation to total inflow. Increasing drainage to compensate for sea level rise, subsidence or intense precipitation would enhance ground water flow into the lake and decrease Cl concentration while increasing evaporation would increase Cl concentration. Groundwater rich in dissolved trace elements flows into the gravel pit lakes that contains water with a higher pH and dissolved oxygen. Pit lake water remains enriched in some elements (e.g., Ba, Mo, Sb) and depleted in others (e.g., Fe, Ca, Zn, SO4) with respect to groundwater composition. The gravel pit lakes show limited eutrophication but the water quality should be monitored for trace elements (e.g., As) if they are to be used for recreational purposes.