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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
Walls of submerged caves feeding Florida springs are often lined with a heavy mat of filamentous bacteria, many of which are able to oxidize reduced sulfur in groundwater migrating from the porous bedrock into the cave conduit. To determine changes in water chemistry as water passes through the microbial mat, a simple device made from standard well screen and sealed with a rubber stopper and controllable vents was installed in a hole drilled in the wall of the cave passage. The sampler was sealed in place with marine epoxy. we measured anions in water from the sampler and from the water-filled conduit taken just outside the sampler. Most anions measured viz., Cl−, NO3−, and PO43−, increased slightly between the matrix and conduit waters. However, traces of sulfide were measured in the water from the rock matrix, but not in the conduit. SO4 2−concentrations in the conduit were about twice that measured in the water from the sampler, about 22 and 11 mg SO42− L−1, respectively, providing further evidence that sulfur oxidation is an important process in the bacterial mats attached to the limestone surfaces in these caves. An additional use of the sampling device is to measure discharge from the local bedrock into the cave conduit.
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