The late Cretaceous Mancos Shale in western Colorado contains several vadose caves developed entirely within the shale. The largest of these, Rock Pigeon Cave, is over 300 m in length and contains a seasonal stream. The cave, and others like it, is hypothesized to develop as a result of the oxidation of disseminated pyrite in the shale by descending meteoric water with resulting sulfate ions reacting with the carbonate component of the shale to produce gypsum. The gypsum pries apart the shale, increasing its secondary porosity, and allows flowing water to remove shale particles via corrasion. As these particles are removed, they are transported down-gradient to an outlet, allowing continuous openings (cave passages) to develop. Extensive sulfate mineralization is observed within the cave and takes several forms: soft globular deposits on rocks at water level, a white to tan crust on shale surfaces, dry crusts on the passage floor following evaporation of pools, and needle and hair-like extrusions on passage walls. Powder X-ray diffraction (XRD) indicates that these deposits are a mixture of thenardite and blodite with lesser amounts of gypsum, hexahydrite, and konyaite. Na+, Mg2+, and SO4 2- ions in the entering stream are the source of the sulfate minerals at stream level and on the wetted slopes above. These come out of solution as the cave stream and pools evaporate with sulfates precipitating as saturation is reached. Fibrous, needle-like sulfates on walls above the wetted zone are a result of crystallization by evaporation: fluids containing sulfate ions are extruded and evaporate at the rock/air interface. Other minerals, e.g., deposits containing goethite and jarosite, are seen on passage walls as reaction products from oxidation of pyrite in the shale.
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