Sulfuric Acid Speleogenesis

(Submitted Abstract to the 2001 AGU Meeting, San Francisco, California)

Sulfuric Acid Speleogenesis: Microbial Karst and Microbial Crust

Annette Summers Engel*, Philip C Bennett, Libby A Stern

The University of Texas at Austin, Department of Geological Sciences, Austin, Texas, 78712

Sulfuric acid speleogenesis is a fundamental mechanism of karst formation, and is potentially responsible for the formation of some of the most extensive cave systems yet discovered. Speleogenesis occurs from the rapid dissolution of the host limestone by sulfuric acid produced from biotic and abiotic sulfide oxidation, and with the release of carbon dioxide, secondary gypsum crusts form. This crust develops predominately on the cave walls, often preserving original bedding indicators, until it finally collapses under its own weight to expose fresh limestone for dissolution. While this general speleogenetic process can be inferred from secondary residues in some caves, directly observing this process is difficult, and involves entry into an extreme environment with toxic atmospheres and low pH solutions.

Kane Cave, Big Horn County, WY, offers the unique opportunity to study microbe-rock interactions directly. Kane Cave presently contains 3 springs that discharge hydrogen sulfide-rich waters, supporting thick subaqueous mats of diverse microbial communities in the stream passage. Condensation droplets and elemental sulfur form on subaerially exposed gypsum surfaces. Droplets have an average pH of 1.7, and are dominated by dissolved sulfate, Ca, Mg, Al, and Si, with minor Sr and Fe, and trace Mn and U. SEM and EDS examination of the crusts reveal the presence of C, O, and S, as well as authigenic, doubly-terminated quartz crystals. The d ¹³C value of –36 permil suggests that the crusts are biogenic and are composed of chemoautotrophic microorganisms. Enrichment cultures of biofilms and acid droplets rapidly produce sulfuric acid, demonstrating the dominance of sulfur-oxidizing bacteria.

Colonization of gypsum surfaces by acidophilic microorganisms enhances acid dissolution of the limestone, and hence the growth of the cave itself. Limestone dissolution also results in mineralized crusts and biofilms that accumulate insoluble residues, which serve as sources of nutrient Fe, P, and N to the microbes. Other elements, such as Si, increase in concentration in the acid solutions and low-temperature mineral precipitation occurs.