Fate of sulfide in the Frasassi cave system and implications for sulfuric acid speleogenesis

• We quantified hydrogen sulfide dynamics in sulfidic cave streams.
• Degassing was the major sink for dissolved sulfide.
• Microbial sulfide oxidation did not appear to result in sulfuric acid production.
• Subaerial sulfuric acid speleogenesis is important for the evolution of sulfidic cave systems.

The oxidation of hydrogen sulfide (H2S) has led to the formation of some of the world's largest caves through a process known as sulfuric acid speleogenesis (SAS). Here we present a multi-year study of the large, sulfidic, and actively-forming Frasassi cave system, Italy. We show that despite the presence of abundant sulfide-oxidizing biofilms in Frasassi streams, H2S(g) degassing to the cave atmosphere was the major sink for dissolved sulfide. Degassing rates ranged from 0.9 to 80 μmol m− 2 s− 1, whereas microbial oxidation rates were between 0.15 and 2.0 μmol m− 2 s− 1. Furthermore, microsensor measurements showed that sulfuric acid is not a major end product of microbial sulfide oxidation in the streams. Our results suggest that subaerial SAS will be important for karstification, and more important than subaqueous SAS, wherever ground waters with high sulfide concentrations emerge as flowing streams in contact with cave air.