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The epikarst is a permeable boundary between surface and subsurface environments and can be conceptualized as the vadose critical zone of epigenic karst systems which have not developed under insoluble cover. From a hydrologic perspective, this boundary is often thought of as being permeable in one direction only (down), but connectivity between the flow paths of water through the epikarst and the root systems of woody plants means that water moves both up and down across the epikarst. However, the dynamics of these flows are complex and highly dependent on variability in the spatial structure of the epikarst, vegetation characteristics, as well as temporal variability in precipitation and evaporative demand. Here we summarize insights gained from working at several sites on the Edwards Plateau of Central Texas, combining isotopic, hydrogeochemical, and ecophysiological methodologies. 1) Dense woodland vegetation at sites with thin to absent soils (0-30 cm) is in part supported by water uptake from the epikarst. 2) However, tree transpiration typically becomes water-limited in dry summers, suggesting that the plant-available fraction of stored water in the epikarst depletes quickly, even when sustained cave drip rates indicate that water is still present in the epikarst. 3) Flow paths for water that feeds cave drips become rapidly disconnected from the evaporation zone of the epikarst and out of reach for plant roots. 4) Deep infiltration and recharge does not occur in these systems without heavy or continuous precipitation that exceeds some threshold value. Thresholds are strongly correlated with antecedent potential evapotranspiration and rainfall, suggesting control by the moisture status of the epikarst evapotranspiration zone. The epikarst and unsaturated zone in this region can be conceptualized as a variably saturated system with storage in fractures, matrix porosity, and in shallow perched aquifers, most of which is inaccessible to the root systems of trees, although woody vegetation may control recharge thresholds.
The oxidation of hydrocarbons and sulfide sources (H2S, pyrite) produces sulfuric acid that strongly reacts with bedrock, causing limestone dissolution and complex interactions with other minerals from the bedrock or from cave fillings, mainly clays. This type of cave development, known as Sulfuric Acid Speleogenesis (SAS), is a subcategory of hypogene speleogenesis, where aggressive water rises from depth. It also produces uncommon minerals, mainly sulfates, the typical byproducts of SAS. Baume Galinière is located in Southern France, in the Vaucluse spring watershed. This small maze cave displays characteristic SAS features such as corrosion notches, calcite geodes, iron crusts, and various sulfate minerals. Sulfur isotopes of SAS byproducts (jarosite and gypsum) clearly show they derive from pyrite oxidation. Using XRD and micro-Raman spectroscopy, thirteen minerals were identified, including elemental sulfur, calcite, quartz, pyrite, goethite, gypsum, fibroferrite, plus all of the six members of the jarosite subgroup (jarosite, argentojarosite, ammoniojarosite, hydroniumjarosite, natrojarosite, plumbojarosite). The Baume Galinière deposits are the first documented cave occurrence of argentojarosite and the second known occurrence of plumbojarosite, hydronium jarosite, ammoniojarosite, and fibroferrite. In the Vaucluse watershed, there were numerous upwellings of deep water along major faults, located at the contact of the karstic aquifer and the overlying impervious covers. The mixing of deep and meteoric waters at shallow depths caused pyrite depositions in numerous caves, including Baume Galinière. Sulfuric acid speleogenesis occurred later after base-level drop, when the cave was under shallow phreatic conditions then in the vadose zone, with oxidation of pyrites generating sulfuric acid. Attenuated oxidation is still occurring through condensation of moisture from incoming air. Baume Galinière Cave records the position of the semi-impervious paleo-cover and documents its retreat in relationship to valley incision caused by uplift and tilting of the Vaucluse block during the Neogene.
The oxidation of hydrocarbons and sulfide sources (H2S, pyrite) produces sulfuric acid that strongly reacts with bedrock, causing limestone dissolution and complex interactions with other minerals from the bedrock or from cave fillings, mainly clays. This type of cave development, known as Sulfuric Acid Speleogenesis (SAS), is a subcategory of hypogene speleogenesis, where aggressive water rises from depth. It also produces uncommon minerals, mainly sulfates, the typical byproducts of SAS. Baume Galinière is located in Southern France, in the Vaucluse spring watershed. This small maze cave displays characteristic SAS features such as corrosion notches, calcite geodes, iron crusts, and various sulfate minerals. Sulfur isotopes of SAS byproducts (jarosite and gypsum) clearly show they derive from pyrite oxidation. Using XRD and micro-Raman spectroscopy, thirteen minerals were identified, including elemental sulfur, calcite, quartz, pyrite, goethite, gypsum, and fibroferrite, plus all of the six members of the jarosite subgroup (jarosite, argentojarosite, ammoniojarosite, hydroniumjarosite, natrojarosite, plumbojarosite). The Baume Galinière deposits are the first documented cave occurrence of argentojarosite and the second known occurrence of plumbojarosite, hydronium jarosite, ammoniojarosite, and fibroferrite. In the Vaucluse watershed, there were numerous upwellings of deep water along major faults, located at the contact of the karstic aquifer and the overlying impervious covers. The mixing of deep and meteoric waters at shallow depths caused pyrite depositions in numerous caves, including Baume Galinière. Sulfuric Acid Speleogenesis occurred later after base-level drop, when the cave was under shallow phreatic conditions then in the vadose zone, with oxidation of pyrites generating sulfuric acid. Attenuated oxidation is still occurring through condensation of moisture from incoming air. Baume Galinière Cave records the position of the semi-impervious paleo-cover and documents its retreat in relationship to valley incision caused by uplift and tilting of the Vaucluse block during the Neogene.
Caves formed by rising sulfuric waters have been described from all over the world in a wide variety of climate settings, from arid regions to mid-latitude and alpine areas. H2S is generally formed at depth by reduction of sulfates in the presence of hydrocarbons and is transported in solution through the deep aquifers. In tectonically disturbed areas major fractures eventually allow these H2S-bearing fluids to rise to the surface where oxidation processes can become active producing sulfuric acid. This extremely strong acid reacts with the carbonate bedrock creating caves, some of which are among the largest and most spectacular in the world. Production of sulfuric acid mostly occurs at or close to the water table but also in subaerial conditions in moisture films and droplets in the cave environment. These caves are generated at or immediately above the water table, where condensation–corrosion processes are dominant, creating a set of characteristic meso- and micromorphologies. Due to their close connection to the base level, these caves can also precisely record past hydrological and geomorphological settings. Certain authigenic cave minerals, produced during the sulfuric acid speleogenesis (SAS) phase, allow determination of the exact timing of speleogenesis. This paper deals with the morphological, geochemical and mineralogical description of four very typical sulfuric acid water table caves in Europe: the Grotte du Chat in the southern French Alps, the Acqua Fitusa Cave in Sicily (Italy), and the Bad Deutsch Altenburg and Kraushöhle caves in Austria
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