Many interesting minerals are found in caves in addition to the calcite which forms the major features. Aragonite, a calcium carbonate mineral similar to calcite but not as common, often occurs in intricate needles known as anthodites. Gypsum (calcium sulfate) and related calcium sulfate minerals are next to calcite in abundance. Some caves, although they are developed in limestone, have extensive passages lined with fine, curling growths of gypsum flowers. In other caves, selenite (a less common variety of gypsum) forms long transparent rods or nests of fibrous crystals. Sulfates of sodium and magnesium are also found in caves, although they are less conspicuous than gypsum. Iron minerals in the form of oxides (limonite) and hydroxide (goethite) occur in caves and in some places form stalactites. Manganese minerals in caves are commonly present as thin, sooty coatings on walls and ceilings and in earth fills. Nitrocalcite (calcium nitrate) is abundant in earth fills in many caves, but individual fragments are generally microscopic. Barite (barium sulfate) and celestite (strontium sulfate) also occur in earth fills. In some solution caves, clay minerals exist in relatively pure forms; these include the less common varieties attapulgite and endellite.

In deep caves encountered during mining operations, a number of ore minerals have been found in the decorative wall draperies. Most common are azurite and malachite (forms of copper carbonate). About 50 other minerals also have been reported in cave deposits.

http://scienceviews.com/geology/caveminerals.html

Like rock varnish, todorokite and birnessite have been identified in the cave deposits along with illite and other clays. Nanocrystalline Fe- and Mn-oxides were confirmed by TEM examination. The oxides show a progression of increasing crystallinity from filamentous forms to fibrous, needle-like crystals to platy crystals. We believe that this progression of Mn-oxidation and crystallization may elucidate similar processes in rock varnish where Mn-coated microbial debris is recrystallized to form the microlaminations that are common in varnish.https://gsa.confex.com/gsa/2002AM/finalprogram/abstract_46060.htm

You could check this paper.

Onac, B.P., Forti, P., 2011. State of the art and challenges in cave minerals studies. Studia UBB Geologia 56, 33–42.

Best

Thanks Fernando!

You could review the following for additional data:

Paul L. Broughton, 1971, Übersicht der in Tropfsteinen bekanntgewordenen Minerale. Die Hӧhle, Zeitschrift für Karst-und Hӧhlenkunde, volume 22, number 3, pages 81-82.

Paul L. Broughton, 1971, Origin and distribution of mineral species in limestone caves. Earth Science Journal (New Zealand), volume 5, number 1, pages 36-43.

Paul L. Broughton, 1972, Monohydrocalcite in speleothems: an alternative interpretation. Contributions to Mineralogy and Petrology, volume 36, number 2, pages 171-174.

Paul L. Broughton, 1972, Secondary mineralization in the cavern environment. Studies in Speleology, volume 2, part 5, pages 191-207. Published by William Pengelly Cave Studies Trust, Buckfastleigh, England

Paul L. Broughton, 1973, Replacement of gypsum by length-slow chalcedony in the karst subsurface. Caves and Karst: Research in Speleology, volume 15, number 3, pages 21-23. (published by Cave Research Associates, ceased publication in 1973)

Paul L. Broughton, 1974, Protodolomite and hydromagnesite in cave deposits of Sumidero Tenejapa, Chiapas, Mexico. Boletín de la Sociedad Venezolana de Éspéleología, volume 5, number 1, pages 19-25.

Thank you Paul!