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The presence of cavities filled with new minerals in carbonate rocks is a common feature in oil reservoirs and lead-zinc deposits. Since groundwater equilibrates rapidly with carbonates, the presence of dissolution cavities in deep carbonate host rocks is a paradox. Two alternative geochemical processes have been proposed to dissolve carbonates at depth: hydrogen sulfide oxidation to sulfuric acid, and metal sulfide precipitation. With the aid of geochemical modeling we show that mixing two warm solutions saturated with carbonate results in a new solution that dissolves limestone. Variations in the proportion of the end-member fluids can also form a supersaturated mixture and fill the cavity with a new generation of carbonate. Mixing is in general more effective in dissolving carbonates than the aforementioned processes. Moreover, mixing is consistent with the wide set of textures and mineral proportions observed in cavity infillings
Five hypogenic-origin caves from Southern France are presented. Investigations using XRD, SEM and Raman spectroscopy, reveal the presence of uncommon cave minerals. Oilloki Cave is a small lead ore mine-cave containing galena, cerussite, and bismuth (present as native element or as sulfide).La Baume Cave is a hydrothermal breccia-pipe, filled with colorful (red, green, white) clays. Some of the clay minerals (clinochlore se-piolite), could originate from hydrothermal weathering of clastic material. The Mala-coste Quarry, harbors a hydrothermal chimney with enlarged vugs lined with calcite spar and filled with iron oxyhydroxides poolfingers (goethite-hematite) and manganese oxides (birnessite, todorokite). Deposition of iron and manganese oxides results of the pH-Eh evolution along the hydrothermal chimney. Pigette Cave is a hydrothermal ver-tical maze with calcite lining and small iron oxyhydroxides and manganese oxides mass-es. The hydrothermal weathering of the walls deposited grains of lithiophorite, barite, and celadonite, which could originate from glauconite. Baume Galinière Cave is a small horizontal maze originating from the oxidation of sulfide masses of pyrite. Beside the common byproducts (gypsum, goethite, sulfur), the six members of the jarosite sub-group are present: jarosite, ammoniojarosite, argentojarosite, hydronium jarosite, natro-jarosite, plumbojarosite, together with fibroferrite. In these caves, three minerals are new cave minerals (bismuth, celadonite, argentojarosite); some others have been men-tioned before only in a few caves worldwide (clinochlore, lithiophorite, ammoniojaro-site, hydronium jarosite, natrojarosite, plumbojarosite, fibroferrite). The mineralogene-sis involves different processes: (i) Deposition in mixing zone from species carried by rising deep flow (barite, galena, bismuth, birnessite, todorokite, lithiophorite); (ii) Hy-drothermal weathering of clay minerals contained in host rock or present as clastic sediments (clinochlore, sepiolite, celadonite); (iii) Oxidation of sulfide masses (goethite, cerussite, jarosite subgroup minerals, fibroferrite).
Hypogean speleogenesis is the main cave formation process in the Frasassi area. The carbon flux represents an important proxy for the evalution of the different speleogenetic processes. The main sources of CO2 in the underground karst system are related to endogenic fluid emissions due to crustal regional degassing. Another important CO2 source is hydrogen sulfide oxidation. A small amount of CO2 is also contributed by visitors to the parts of the cave open to the public.
Carbonate minerals comprise the largest reservoir of carbon in the earth’s lithosphere, but they are generally assumed to have no net impact on the global carbon cycle if rapid dissolution and precipitation reactions represent equal sources and sinks of atmospheric carbon. Observations of both terrestrial and marine carbonate systems indicate that carbonate minerals may simultaneously dissolve and precipitate within different portions of individual hydrologic systems. In all cases reported here, the dissolution and precipitation reactions are related to primary production, which fixes atmospheric CO2 as organic carbon, and the subsequent remineralization in watersheds of the organic carbon to dissolved CO2. Deposition of carbonate minerals in the ocean represents a flux of CO2 to the atmosphere. The dissolution of oceanic carbonate minerals can act either as a sink for atmospheric CO2 if dissolved by carbonic acid, or as a source of CO2 if dissolved through sulfide oxidation at the freshwater-saltwater boundary. Since dissolution and precipitation of carbonate minerals depend on ecological processes, changes in these processes due to shifts in rainfall patterns, earth surface temperatures, and sea level should also alter the potential magnitudes of sources and sinks for atmospheric CO2 from carbonate terrains, providing feedbacks to the global carbon cycle that differ from modern feedbacks.
No-mount Cave, located in wekiwa Springs State Park in central Florida, USA, is an aphotic, submerged, freshwater cave in which large colonies of sulfur-oxidizing bacteria live in filamentous microbial mats. Upwardly discharging groundwater enters the cave from the Upper Floridan aquifer, specifically the Eocene-aged Ocala Limestone. we undertook a combined field, laboratory, and modeling study in which we sought to determine the amount of calcite dissolution attributable to the generation of protons by microbially mediated sulfide oxidation. The chemical compositions of groundwater within the limestone formation collected through a newly designed sampling device and of water in the cave conduit were used in geochemical modeling. we used the reaction-path model PHREEqCI to quantify the amount of calcite dissolution expected under various plausible scenarios for mixing of formation water with conduit water and extent of bacterial sulfide oxidation. Laboratory experiments were conducted using flow-through columns packed with crushed limestone from the study site. Replicate columns were eluted with artificial groundwater containing dissolved HS- in the absence of microbial growth. without biologically mediated sulfide oxidation, no measurable calcite dissolution occurred in laboratory experiments and no additional amount of speleogenesis is expected as formation water mixes with conduit water in the field. In contrast, significant calcite dissolution is driven by the protons released in the biological transformation of the aqueous sulfur species. Although a range of results were calculated, a plausible amount of 158 mg Ca2+ released to conduit water per liter of groundwater crossing the formation-conduit boundary and mixing with an equal volume of conduit water was predicted. Our modeling results indicate that significant cave development can be driven by microbially mediated sulfide oxidation under these hydrogeochemical conditions