Abstract:
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.