Source: NOVA "The Mysterious Life of Caves"
The most common process by which limestone caves form involves carbonic acid — or weakly acidic groundwater — as the primary agent. When carbonic acid contacts limestone, it dissolves minerals in the rock. If enough water to saturate the rock is present over a long time period, cavities and entire underground cave networks can form. Recently, a radical new theory has been proposed that identifies another cave-forming agent: sulfuric acid. This video segment adapted from NOVA identifies the mysterious source of the sulfuric acid, which, unlike carbonic acid, does not readily form in nature.
As certain chemical elements cycle through an ecosystem, they interact with both living (bio-) and nonliving (geo-) components of the ecosystem. These elements are recycled within the system in what are known as biogeochemical cycles. Sometimes, however, they are stored for long periods of time outside the pathway in what is called a sink. Examples of carbon sinks include rainforests and caves.
Biogeochemical cycles and atmospheric changes are often linked. Global warming, for example, is a disturbance caused by deforestation and the burning of fossil fuels, which together have altered the carbon balance in the atmosphere. But biogeochemical cycles can also shape the very ground on which we walk. When plants and animals die, their organic compounds combine with oxygen, and the compounds decay. The fraction of compounds that isn't oxidized can, over millions of years, form deposits that convert to coal, petroleum, or peat. Also, shells of dead aquatic animals accumulate on the sea floor and are compressed over time to form limestone, a common surface rock.
Solution caves are typically formed by a chemical reaction between limestone and groundwater that has become slightly acidified through contact with the carbon dioxide present in most soils. The acidified groundwater — called carbonic acid — gradually dissolves away minerals as it invades cracks in the rock. If enough water is available, narrow openings can slowly widen into large cavities and passages.
Now, a radical new theory suggests an agent other than carbonic acid may be responsible for creating some of the largest cave systems in the world. Scientists have discovered that sulfur, not carbon, was responsible for carving out massive cavities from the limestone rock of Capitan Reef, the fossil reef that contains New Mexico's Carlsbad Caverns.
Certain bacteria convert organic sulfur found in oil to hydrogen sulfide gas. Several million years ago, when this gas escaped from oil deposits underlying Capitan Reef, it mixed with oxygen in the groundwater supplies and produced sulfuric acid. Sulfuric acid is capable of dissolving vast amounts of limestone minerals — far more than carbonic acid can — and enough to explain the size of Big Room, which is featured in this video segment. As Capitan Reef uplifted little by little from its origins below sea level, the level of the water table dropped in relation to the land surface. The acidic groundwater drained away to reveal a dissolved cave system with large gypsum deposits, a telltale by-product of a reaction between sulfuric acid and limestone.