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Some of the most outstanding hypogenic gypsum speleothems worldwide have been recently discovered in the Naica mines. The Cueva de las Espadas (Swords Cave), which lies at 120 m depth, hosts a rare type of speleothem called “espada” (“sword”). This study contributes to the understanding of the mineralogical composition of these singular speleothems, by means of their examination using micro-Raman spectroscopy, FT-IR spectroscopy and EDX microprobe. Our data revealed a complex mineralogy comprising a high-purity selenite core covered by several layers of calcite, aragonite and gypsum. Solid inclusions of polymetallic oxides (Mn-Pb-Zn) and graphite were also detected. The position of the water table during the genesis of the “espada” speleothems (over the past 60 kyr) was deduced from their mineralogy. Water level fluctuations at around -120 m depth led to environmental changes within the Cueva de las Espadas. The selenite core and gypsum layers were precipitated under biphasic (water-rock) conditions when the cave was submerged under hydrothermal water. The aragonite precipitation required triphasic (air-water-rock) conditions and occurred when the water table intercepted the cave, allowing the CO2 exchange necessary for carbonate precipitation. Solid inclusions were trapped in an aerobic environment when the gypsum-aragonite boundary condition occurred. A thin calcite layer was precipitated under vadose conditions after the water table definitively moved out of the cave.

Unusual amberine-coloured speleothems were recently found in El Soplao Cave (Cantabria, Spain). Chromophore elements such as Fe, Mn, Cd, Co or Ti were not present in significant quantities. Rather, our data show that their colour comes from leachates of fossilized organic material hosted in the carbonaceous Urgonian facies of the host rock. These leachates are related to the Cretaceous amber deposit that has been recently discovered in the vicinity of El Soplao Cave. The presence of humic and fulvic acids of fossil origin were confirmed by IR and Raman spectroscopic analysis of the carbonaceous strata and the speleothems. In addition, the mineralogy of the amberine speleothems was studied. Alternating bands made of calcite and aragonite reveal that periods of humidity and aridity occurred within the cave during the speleothem genesis.

Perhaps man’s first motivation to explore caves, beyond using them as shelter, was the search for substances that were not availableelsewhere: most of them were minerals. However, for a long time it was believed that the cave environment was not very interestingfrom the mineralogical point of view. This was due to the fact that most cave deposits are normally composed of a singlecompound: calcium carbonate. Therefore, the systematic study of cave mineralogy is of only recent origin. However, although onlya limited number of natural cavities have been investigated in detail, about 350 cave minerals have already been observed, someof which are new to science. The presence of such unexpected richness is a direct consequence of the variety of rocks traversedby water or other fluids before entering a cave and the sediments therein. Different cave environments allow the development ofvarious minerogenetic mechanisms, the most important of which are double exchange reactions, evaporation, oxidation, hydrationdehydration,sublimation, deposition from aerosols and vapors, and segregation. The cave temperature and pH/Eh strictly controlmost of them, although some are driven by microorganisms. The cave environment, due to its long-term stability, can sometimesallow for the development of huge euhedral crystals, such as those found in the Naica caves (Mexico), but the presence of extremelysmall yet complex aggregates of different minerals is far more common. Future development in the field of cave mineralogy will likelybe focused mainly on hydrothermal and sulfuric-acid caves and on the role played by micro-organisms in controlling some of the mostimportant minerogenetic processes in caves.

Ojo de la Reina is the first and the smallest cave intersected at the -290 level in the Naica Mine (Mexico), therefore it was the firstcavity in which the lowering of temperature induced by mine ventilation caused condensation over crystals’ surface since 2005. Theconsequent dissolution of the gypsum crystals and subsequent condensed water evaporation lead to the deposition of several newminerals, among which some highly soluble Mg/Na compounds (bloedite, epsomite, halite, hexahydrite, kieserite, starkeyite). Thesingle available source of Mg and Na ions in this minerogenetic environment is represented by the huge fluid inclusions widespreadwithin the crystals. The condensation occurs mainly along the widened principal exfoliation (010) planes, and allows to an easy andfast opening of the fluid inclusions that consequently drip Mg-rich fluids stored inside them. Finally the evaporation of the relativelysmall volumes of involved water allows to the development of the high soluble Mg and Na compounds.

Peculiar iron and manganese deposits coating walls, floors and ceilings of many galleries are one of the special features of the ElSoplao Cave (Cantabria, Spain). These speleothems appear to have been deposited over wall clay deposits, as well as formingpart of flowstones. Structure of crusts is essentially amorphous but several manganese and iron oxides were identified like goethiteand birnessite, though all occur with a low degree of crystallinity. In the outer layer of the crusts, alteration iron minerals appear thatderive from previous minerals in a process probably mediated by microorganisms. EDX microanalyses report fairly high values of Feand Mn in the crusts, though the Mn/Fe ratio varies considerably as a function of distance from the substrate/bedrock. The presentstudy proposes a genetic model for crust speleothems in El Soplao, based on oscillations of the phreatic level. The origin of thesedeposits is related to mobilization, under phreatic conditions, of polymetallic sulfides in the host rock. Metal ions (including Fe²+ andMn²+) released into the cave under reducing conditions, are oxidized and fixed in a process mediated by bacteria, giving rise to oxidesand hydroxides of low crystallinity. The presence of various black intercalated layers in aragonite flowstones indicate periods whencave conditions suddenly changed from vadose, when aragonite is precipitated, to phreatic and epiphreatic conditions, when theMn-Fe deposits are precipitated. Subsequently, vadose conditions were re-established, leading to the final stages of precipitation ofaragonite recorded in the flowstone and recent aragonite helictites on the surface of the Mn-Fe crusts.

The analytical problems of dating gypsum speleothems with the U-series technique are reviewed. Gypsum speleothems are, in general, very low in U content, challenging the limits of detection methods. Various approaches to dissolving gypsum and isolation of actinides from the matrix include ion-pairing dissolution with magnesium salts and using nitric acid. The most precise dating technique is Thermal Ionization Mass Spectrometry (TIMS), combined with Fe(OH)3 scavenging and anionic exchange chromatography. Less satisfactory, but much quicker, is direct retention of actinides from HNO3 by means of TRU resin and MC-ICP-MS detection. We have tested these methods on gypsum speleothems from the Sorbas karst in Spain and from the Naica caves in Mexico.

The caves of Naica (Chihuahua, Mexico) are perhaps the most famous mine caves of the world due to the presence of giganticgypsum crystals. Nevertheless, very little research has been carried out on this karst area until now. A multidisciplinary investigationstarted in 2006 with the aim not only to define the genesis and the age of the Naica gypsum crystals, but also on other scientificaspects of these caves.This paper describes a completely new type of gypsum speleothem: the “sails”, observed only inside the Cueva de las Velas, one ofthe caves of the Naica system. This speleothem consists of extremely thin, elongated skeleton crystals that have grown epitaxiallyonly on the tips of the gypsum crystals pointing upward. The genesis of sails is strictly related to the environmental conditions setup inside the cave just after the artificial lowering of the groundwater by mine dewatering (less than 20 yr ago). In a few years sail speleothems will disappear entirely and therefore this study is fundamental to preserve at least the memory of them.

Kenya is one of the few countries in which karst cavities are scarce with respect to volcanic ones, which are widespread throughout the whole country. The great variability in lava composition allowed the evolution of very different cavities, some of which are amongst the largest lava tubes of the world. As normal for such a kind of cave, the hosted speleothems and cave minerals are scarce but important from the minerogenetic point of view. Anyway up to present no specific mineralogical research have been carried out therein. During the 8th International Symposium on Volcanospeleology, held in Nairobi in February 1998, some of the most important volcanic caves of Kenya have been visited and their speleothems and/or chemical deposits sampled: most of them were related to thick guano deposits once present inside these cavities. Speleothems mainly consisted of opal or gypsum, while the deposits related to guano often resulted in a mixture of sulphates and phosphates. The analyses confirmed the great variability in the minerogenetic mechanisms active inside the volcanic caves, which consequently allow the evolution of several different minerals even if the total amount of chemical deposit is scarce. Among the observed minerals kogarkoite, phillipsite and hydroxyapophyllite, must be cited because they are new cave minerals not only for the lava tubes of Kenya, but also for the world cave environment. The achieved results are compared with the available random data from previous literature in order to allow an updated overview on the secondary cave minerals of Kenya.

The idea that speleothems may be somehow influenced by living organisms is rather old, but specific studies have only started in the last few decades and presently there are only a couple of systematic papers on this topic. The role of micro-organisms is perhaps the best investigated even if it is not fully understood, while studies over upper organisms and speleothems in a cavern environment are scarce and details are not always given on the involved genetic mechanisms. The aim of the present paper is to give an updated overview on these topics in order to enhance the interest of the scientific community. In fact the complex biochemical reactions involved in the development of the different cave deposits, though still not well understood, clearly have an interest and an importance far exceeding the simple speleogenetic interest.

The luminescence of calcite speleothems displays an exponential dependence on soil temperature unless there is a dense cover of forest over the cave to dampen it. This relationship is determined primarily by the strength of solar visible and infrared radiation. It is suggested that, as a consequence, the microzonal variations of luminescence often found in speleothems can be used as a proxy index of Solar Insolation. The luminescence solar insolation proxy record of a speleothem from Jewel Cave, South Dakota, USA, was found to display millenial and centennial cycles in the record. It exhibits a rapid increase in solar insolation at 139 ± 5.5 kyrs. This increase precedes that suggested by the Orbital theory by about 10,000 years and is due to superimposition of the most powerful cycle in solar luminosity of 11.5 kyrs, upon the curve of orbital variations. The record from a speleothem in Duhlata Cave, Bulgaria matches that of South Dakota within the limits of dating error, indicating that both of these records (which are 10,000 km apart) measure global solar insolation controls rather than local paleotemperature variations.

The Perolas-Santana karst system (Sào Paulo State, Brazil) has been partially studied from the mineralogical point of view. The present paper will contribute to the knowledge of the minerals in these caves, describing the occurrence of euhedral celestite crystals and of a rather rare mineral for a cavern environment: lithiophorite. Thanks to these new discoveries the Perolas-Santana karst system becomes one of the most important in Brazil from a mineralogical point of view. Finally, the result of the chemical analyses carried out on this newly discovered Monoxyhydroxide put in evidence a zonation in the distribution of the different elements which may be related to several subsequent depositional events characterized by solutions with a chemical content variable in time.