Microbe-mineral affinity in sulfuric acid karst systems

Microbial communities influence the kinetics and pathways of reactions involved in the dissolution of a number of minerals (Ehrlich 1996). On a smaller scale these interactions can affect substrate permeability, porosity, and create highly localized biogeochemical conditions. However, a mechanistic understanding of the consequences of microbial surface colonization on calcite dissolution rate has yet to be achieved. More specifically, little is known about the impact of sulfur-oxidizing bacteria activity on the rate of carbonate mineral dissolution, or the nature of the microbe-limestone attachment and interaction. Through a series of laboratory and field experiments the effect of mineral surface colonization by microbial communities, obtained from an active sulfuric acid cave (Lower Kane Cave (LKC), Big Horn Basin, WY), on the dissolution rate of Madison Limestone was quantified. Results from laboratory experiments showed that a microbial biofilm, composed primarily of Epsilonproteobacteria and Gammaproteobacteria growing on a limestone surface oxidized thiosulfate and increased carbonate dissolution rates up to 3.3 times faster than abiotic rates. When all thiosulfate substrate was withheld the community oxidized stored intracellular sulfur, continuing to accelerate limestone dissolution and decreasing pH. This process is sensitive to O2 limitations. Characterization of this aggressive sub-biofilm corrosion was more closely examined by SEM imaging. By comparing mineral surface morphology of colonized chips to non-colonized chips of various carbonate substrates, it was shown that even under conditions near equilibrium with calcite, aggressive dissolution of carbonate substratum occurs exclusively beneath the biofilm. These findings support the hypothesis that (1) sulfur-oxidizing microbial communities aggressively dissolve carbonates in order to buffer the production of excess acidity by neutrophilic communities and (2) biofilm presence affects carbonate mineral dissolution by physically separating a bulk stream water from the sub-biomat environment. Furthermore, it was found that mineralogy affects the degree of establishment of microbial communities in this environment. Results from a series of four laboratory and one in situ reactor experiment showed that limestone and dolostone substratum consistently had higher biomass accumulations than silicate minerals or pure Iceland spar calcite in the same reactor. These results provide evidence to support the hypothesis that mineralogy influences microbial accumulation in sulfuric-acid karst systems. Particularly, neutrophilic sulfur-oxidizing communities accumulate in greater quantities on solid substrates that buffer metabolically-generated acidity. These results also demonstrated the dependence of microorganisms on colonization of a particular mineral surface, possibly in order to gain access to micronutrients bound within solid substrates when exposed to nutrient-limited conditions.