THE OCCURRENCE AND EFFECT OF SULFATE REDUCTION AND SULFIDE OXIDATION ON COASTAL LIMESTONE DISSOLUTION IN YUCATAN CENOTES, 1993, Stoessell R. K. , Moore Y. H. , Coke J. G. ,

Dissolution of carbonate minerals in the coastal halocline is taking place in the karst terrain along the northeastern coast of the Yucatan Peninsula. The dissolution is being accelerated in cenotes (sinkholes) where sulfate reduction and oxidation of the produced sulfide is occurring. Hydrogen-sulfide concentrations ranged from 0.06 to 4 mmolal within the halocline in two sinkholes. Relative to concentrations expected by conservative mixing, fluids with high hydrogen-sulfide concentrations were correlated with low sulfate concentrations, high alkalinities, low pH values, and heavy sulfur isotope values for sulfate. Hydrogen-sulfide concentrations were less than those predicted from sulfate reduction, calculated from deficiencies in measured sulfate concentrations, indicating mobility and loss of aqueous sulfide. Fluids with low hydrogen-sulfide concentrations were correlated with very high calcium concentrations, high strontium and sulfate concentrations, slightly elevated alkalinities, low pH values, and sea-water sulfur isotope values for sulfate. Gypsum dissolution is supported by the sulfur isotopes as the major process producing high sulfate concentrations. However, oxidation of aqueous sulfide to sulfuric acid, resulting in carbonate-mineral dissolution is needed to explain the calcium concentrations, low pH values, and only slightly elevated alkalinities. The halocline may trap hydrogen sulfide that has been stripped from the underlying anoxic salt water. The halocline can act as a stable, physical boundary, holding some of the hydrogen sulfide until it is oxidized back to sulfuric acid through interaction with the overlying, oxygenated fresh water or through the activity of sulfide-oxidizing bacteria

DETRITAL ORIGIN OF A SEDIMENTARY FILL, LECHUGUILLA CAVE, GUADALUPE MOUNTAINS, NEW MEXICO, 2000, Foos Am, Sasowsky Id, Larock Ej, Kambesis Pn,

Lechuguilla Cave is a hypogene cave formed by oxidation of ascending hydrogen sulfide from the Delaware Basin. A unique sediment deposit with characteristics suggesting derivation from the land surface, some 285 m above, was investigated. At this location, the observed stratigraphy (oldest to youngest) was: bedrock floor (limestone), cave clouds (secondary calcite), calcite-cemented silstone, finely laminated clay, and calcite rafts. Grain-size analysis indicates that the laminated clay deposits are composed of 59-82% clay-size minerals. The major minerals of the clay were determined by X-ray diffraction analysis and consist of interstratified illite-smectite, kaolinite, illite, goethite, and quartz. Scanning electron microscopy observations show that most of the clay deposit is composed of densely packed irregular-shaped clay-size flakes. One sample from the top of the deposit was detrital, containing well-rounded, silt-size particles. Surface soils are probably the source of the clay minerals. The small amount of sand- and silt-size particles suggests that detrital particles were transported in suspension. The lack of endellite and alunite is evidence that the clays were emplaced after the sulfuric-acid dissolution stage of cave formation. Fossil evidence also suggests a previously existing link to the surface

The hypogenic caves: a powerful tool for the study of seeps and their environmental effects, 2002, Forti P, Galdenzi S, Sarbu Sm,

Research performed in caves has shown the existence of significant effects of gas seeps, especially CO2 and H2S, within subterranean voids. Carbon dioxide causes important corrosive effects and creates characteristic morphologies (e.g., bell-shaped domes, bubble's trails), but is not involved in the deposition of specific cave minerals. On the other hand, in carbonate environments, hydrogen sulfide when oxidized in the shallow sections of the aquifer generates important corrosion effects and is also responsible for the deposition of specific minerals of which gypsum is the most common.Studies performed in the last few years have shown that H2S seeps in caves are associated with rich and diverse biological communities, consisting of large numbers of endemic species. Stable isotope studies (carbon and nitrogen) have demonstrated that these hypogean ecosystems are entirely based on in situ production of food by chemoautotrophic microorganisms using energy resulting from the oxidation of H2S.Although located only 20 m under the surface, Movile Cave does not receive meteoric waters due to a layer of impermeable clays and loess that covers the Miocene limestone in which the cave is developed. In the Frasassi caves, where certain amounts of meteoric water seep into the limestone, the subterranean ecosystems are still isolated from the surface. As the deep sulfidic waters mix with the oxigenated meteoric waters, sulfuric acid limestone corrosion is accelerated resulting in widespread deposition of gypsum onto the cave walls.Both these caves have raised a lot of interest for biological investigations regarding the chemoautotrophically based ecosystems, demonstrating the possibility of performing such studies in environments that are easily accessible and easy to monitor compared to the deep-sea environments where the first gas seeps were discovered