There are three broad categories of sedimentary material found in caves: clastic sediments carried in by streams and infiltrated from the surface; blocks, slabs, and fragments of breakdown derived from the local bedrock; and chemical sediments deposited in the cave by percolating waters. The chemical sediments are the most diverse and are responsible for the decorative beauty of many caves.
The most common of the secondary chemical sediments is calcite, calcium carbonate. There also occurs a less common form of calcium carbonate, the mineral aragonite. The second most common cave mineral is gypsum, calcium sulfate dihydrate. Other carbonate, sulfate, and oxide minerals are occasionally found in caves as well. Many of these require that the cave be associated with ore deposits or with other special geologic environments. For this reason, of the more than 200 mineral species known to occur in caves, only about 20 are found widely.
Deposits of cave minerals occur in many forms, their shapes determined by whether they were deposited by dripping, flowing, or seeping water or in standing pools of water. Collectively, these secondary mineral forms are known as speleothems.
Water emerging from a joint in the cave ceiling hangs for a while as a pendant drop. During this time, a small amount of calcium carbonate is deposited in a ring where the drop is in contact with the ceiling. Then the drop falls, and a new drop takes its place, also depositing a small ring of calcium carbonate. In this manner, an icicle-like speleothem called a stalactite is built up. Stalactites vary in shape from thin strawlike features to massive pendants or drapery-like forms. Stalactites have a central canal that carries water from the feeder joint to the stalactite tip. When the drops fall to the floor of the cave, additional mineral matter is deposited and stalagmites are built up. Stalagmites also take on many forms, from slender broom-handle to mound- and pagoda-like shapes. Stalagmites consist of superimposed caps or layers and do not have a central canal. Stalactites may grow so large that they cannot support their own weight; the broken fragments of large stalactites are sometimes found in caves. Stalagmites are not so restricted and can reach heights of tens of metres. Water flowing along ledges and down walls leaves behind sheets of calcite, which build up a massive deposit known as a flowstone.
Most flowstone deposits are composed of calcite, though other minerals occasionally are present. The calcite is usually coarsely crystalline, densely packed, and coloured various shades of tan, orange, and brown. Some of the pigment is from iron oxides carried into the deposit by the seepage water, but the more common colouring agent is humic substances derived from overlying soils. Humic substances are the organic products of plant decay, which are also responsible for the brown colour of some soils and for the tealike colour of some swamp and lake waters. Calcite speleothems may be pure white but appear milky because of many tiny inclusions of water within the structure.
The calcite in speleothems is derived from the overlying limestone near the bedrock/soil interface. Rainwater infiltrating through the soil absorbs carbon dioxide from the carbon dioxide-rich soil and forms a dilute solution of carbonic acid. When this acid water reaches the base of the soil, it reacts with the calcite in the limestone bedrock and takes some of it into solution. The water continues its downward course through narrow joints and fractures in the unsaturated zone with little further chemical reaction. When the water emerges from the cave roof, carbon dioxide is lost into the cave atmosphere and some of the calcium carbonate is precipitated. The infiltrating water acts as a calcite pump, removing it from the top of the bedrock and redepositing it in the cave below.
Caves provide a very stable environment where temperature and relative humidity may remain constant for thousands of years. The slow growth of crystals is not interrupted, and some speleothems have shapes controlled by the forces of crystal growth rather than by the constraints of dripping and flowing water. Speleothems known as helictites are much like stalactites in that they have a central canal and grow in long tubular forms. They twist and turn in all directions, however, and are not guided by the gravitational pull on pendant water drops. Another variety of speleothem, the anthodite, is a radiating cluster of needlelike crystals. Anthodites are usually composed of aragonite, which has a different habit (i.e., shape of individual crystal grains) than the more common variety of calcium carbonate, calcite. Layered bead or corallike forms occur on cave walls, and complex arrangements of crystals are found in cave pools. Pools of water saturated with calcium carbonate have the remarkable property of surrounding themselves with rimstone dams of precipitated calcite.
Gypsum and other more water soluble sulfate minerals such as epsomite (magnesium sulfate heptahydrate) and mirabilite (sodium sulfate decahydrate) grow from seepage waters in dry caves. Deposition of the sulfate minerals is due to evaporation of the mineral-bearing solutions. These minerals occur as crusts and in the form of radiating, curving masses of fibrous crystals known as gypsum flowers. Because of their higher solubility, sulfate minerals either do not occur or are destroyed in damp or wet caves.