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Carbonate cave deposits (speleothems) have been used widely for paleoclimate reconstructions; however, few studies have examined the utility of other speleothem-forming minerals for this purpose. Here we demonstrate for the first time that stable isotopes (δ17O, δ18O and δD) of structurally-bound gypsum (CaSO4·2H2O) hydration water (GHW) can be used to infer paleoclimate. Specifically, we used a 63 cm-long gypsum stalactite from Sima Blanca Cave to reconstruct the climate history of SE Spain from ~ 800 BCE to ~ 800 CE. The gypsum stalactite indicates wet conditions in the cave and humid climate from ~ 200 BCE to 100 CE, at the time of the Roman Empire apogee in Hispania. From ~ 100 CE to ~ 600 CE, evaporation in the cave increased in response to regional aridification that peaked at ~ 500–600 CE, roughly coinciding with the transition between the Iberian Roman Humid Period and the Migration Period. Our record agrees with most Mediterranean and Iberian paleoclimate archives, demonstrating that stable isotopes of GHW in subaerial gypsum speleothems are a useful tool for paleoclimate reconstructions.

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Caves are generally very stable spaces, but easily alterable from the environmental point of view. In show caves, the geochemical rock-atmosphere interface in carbonate karst caves can be affected by tourism. In this regard, the influence of tourism on the increase of CO2 concentration is particularly important. Therefore, knowing the visitor influx that guarantees the maintenance of the natural balance of show caves is of special interest from the point of view of management and conservation. In this paper, a novel method to determine the maximum recommended number of visitors in periods of a massive influx of tourists in show caves is proposed. This method consists of relating the CO2 level, its derivative and the presence of visitors by means of a linear model. Afterwards, an initial value problem to predict the CO2 concentration throughout the day is established, using the expected pattern of visits and the CO2 concentration at the beginning of the day as inputs. The results show an excellent performance when used as a descriptive model (correlation coefficient R ≈ 0.99 with respect to the actual values), and as a predictive model (R ≈ 0.95). Once the global predictive model has been learned, it can be used to make predictions about the CO2 levels in any other future events. Thus, the proposed method allows running simulations of different regimes of visits (for instance, limiting the desired maximum level of CO2), allowing cave managers to determine the best regime for a specific cave. Therefore, this method can be useful to minimize the impact of tourism on show caves while maximizing its visitor capacity, helping to protect underground ecosystems.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

This article reviews the state of the art of speleogenetic investigations in gypsum karsts from numerous studies carried out over the past 50 years in Spain. A classification of gypsum karsts is proposed based on the hydrogeological, tectonic and stratigraphic criteria that decisively control the evolution of gypsum karsts. In this respect, lithological aspects of Messinian and Triassic-Permian gypsum series in south-eastern Spain are considered, such as the alternation of rhythmic levels of marl and gypsum, as well as geodynamic aspects. The influence of the hydrogeological characteristics of evaporite aquifers on gypsum cave speleogenesis is discussed; this includes speleogenetic processes in confined, semi-confined or free aquifers controlled by regional and local base levels. Also, the importance of intense saline diapiric uplift is examined. To illustrate our classification, examples of gypsum caves developed in Spain are presented. Their similarities and differences with gypsum karsts in other regions (Italy, Ukraine, and USA) are discussed. A first general division addresses: (1) caves controlled by stratigraphic factors and (2) caves controlled by tectonic factors. Several typologies can be described, including (A) multilayer caves with confined hydrogeological origin, (B) confined hypophreatic caves with linear or maze configurations, (C) caves controlled by the variation or remanence of regional or local base-levels, and (D) caves controlled by the halokinetic evolution of salt/gypsum diapirs. The proposed classification is flexible and adaptable to each case, because different genetic mechanisms can coincide in time and space. Likewise, most considerations stated in this work about gypsum karst are valid for speleogenesis in other rock types. Publisher PDF

Gypsum (CaSO4∙2H2O) speleothems (i.e. stalactites, stalagmites, etc.) in caves form frequently through dissolution of the gypsum host-rock by seepage water and subsequent secondary mineral re-precipitation from gypsum-saturated solutions [1]. Gypsum takes its structurally-bound hydration water (GHW) from the liquid; the isotopic composition (δ17O, δ18O and δ2H) of GHW reflects that of cave dripwater at the time of mineral crystallization, with insignificant effect of temperature on the liquid-GHW isotope fractionation factors [2]; therefore, GHW may be used to reconstruct the isotopic composition of paleo-dripwater in caves. Here we investigate the triple oxygen and hydrogen isotopic composition of GHW in speleothems from circum-Mediterranean gypsum caves, including the gypsum karsts of Emilia Romagna (NE Italy), Sorbas (SE Spain), Sicily and Mesaoria (Cyprus), all of them hosted in gypsum of Messinian age (ca. 5.5 Ma). The climatic settings of the studied caves range from semiarid (i.e. Sorbas and Mesaoria, -1) to relatively wet (i.e. Emilia Romagna and Sicily >600 mm·yr-1).Our results reveal that most gypsum speleothems in these caves precipitated from unevaporated solutions (e.g. d-excess >8‰ and 17Oexcess >10 per meg), with isotopic compositions similar to those of local meteoric/seepage waters and close to the local meteoric water lines (LMWL) of each region. Gypsum crystallization in absence of evaporation can be explained by the mechanism known as Ostwald ripening [3], a solution-mediated recrystallization under constant temperature by which older crystals (i.e. Messinian gypsum) dissolve to feed new crystals (i.e. gypsum speleothems). Only GHW in speleothems from the Sorbas caves show evidence for solution evaporation prior mineral precipitation. Gypsum speleothems in several caves of Emilia Romagna crystallized from unevaporated waters with significantly different triple oxygen and hydrogen isotopic compositions (e.g. Ca´ Castellina cave: δ18O=-8.3±0.3‰, δ2H=-55.2±1.7‰, 17Oexcess=33±9 per meg; Abisso Bentini cave: δ18O=-10.6±0.3‰, δ2H=-73.4±1.8‰, 17Oexcess=47±13 per meg). In absence of chronological data, this can be interpreted as (1) gypsum speleothems formed in different climatic periods or (2) do at present from waters that seepage into the epikarst during different times of the year. Either way, gypsum records the mean isotopic composition of seepage water under distinct environmental conditions in this region.The δ18O and 17Oexcess values across the entire dataset are negatively correlated, unlike δ18O and d-excess values that are, positively correlated for δ18O18O>-6‰. We suggest that the different behaviors of 17Oexcess and d-excess derive from their distinct sensitivities to environmental parameters (i.e. RH and temperature) during formation of water vapor at the moisture source of rain and local effects during rainfall events in each area. We conclude that gypsum speleothems of known ages may be useful as archives for triple oxygen and hydrogen isotope reconstructions of paleo-rainfall.[1] Gázquez et al. 2017. Chemical Geology, v. 452, p. 34–46; [2] Gázquez et al. 2017. Geochimica et Cosmochimica Acta, v. 198, p. 259–270; [3] Kahlweit, 1975. Advances in Colloid and Interface Science, v. 5, p. 1–35.

On-line, del 4 al 8 de mayo de 2020, The hydrothermal caves linked to active faulting have subterranean atmospheres with a distinctive gaseous composition containing deep endogenous gases, such as carbon dioxide, methane and nitrogen oxides (NOx). Ascending fluids through associated near-surface hydrothermal processes can mobilize endogenous gases into the Critical Zone and, ultimately, to the lower troposphere. Nitrogen oxides are polluting gases and can have adverse effects on human health, especially inhaled NO2. They also catalyse ozone (O3) production in the lower layers of the atmosphere and the greenhouse effect, when they react with volatile organic compounds. The largest source of NOx emissions is anthropogenic. The rest is produced naturally by microbial processes in soil and water, by lightning, volcanic activity, storms, etc. Production of N2O and NO2 is associated with soil and other active-geothermal ecosystems, far less is known about the sources and sinks of these gases within subterranean locations. Here, we report high N2O and NO2 concentrations detected along a hypogenic system associated with an active faulting (Vapour Cave, southern Spain), which enables direct gas exchange with the low-atmosphere. These anomalous concentrations of N2O and, NO2 are about ten and five times higher than the typical atmospheric background, respectively. Gaseous composition analyses of subterranean atmosphere were conducted by high precision field-deployable CRDS and FTIR spectrometers for measuring in situ the target tracer gases (NO2, N2O, CH4, CO2) and ¿13C of both carbon-GHGs. DNA extraction, sequencing and phylogenetic analyses were conducted to characterize the microbial community of cave sediments. The results showed that N2O and NO2 emission depends on the activity of nitrification by ammonia oxidizing microorganisms (such as members of the family Nitrosomonadaceae and phylum Thaumarchaeota) and/or as a result of incomplete denitrification by heterotrophic denitrifying bacteria (such as Bacillus, Acinetobacter and Cupriavidus) from this hydrothermal and hypoxic ecosystem. On the other hand, CH4 concentrations and 13CH4 vary along the cave (with the deep), in deepest cave locations CH4 values are higher with lighter 13C values in comparison with the more superficial areas, which indicates a deep endogenous origin of methane. However, in areas near the entrance we observe lower concentrations of methane and heavier 13C values (CH4

We analyzed the stable isotopes (δ 17 O, δ 18 O and δD) of gypsum hydration water (GHW) in a variety of speleothems, as well as condensation and infiltration waters in five caves of the semiarid gypsum karst of Sorbas basin (Almeria, SE Spain). Microclimate parameters (air temperature, relative humidity and effective condensation rate) were also monitored over an annual cycle. We found that the mother solution from which the majority of gypsum speleothems grow is composed of a mixture of condensation (~ 60%) and infiltration water (~ 40%) that undergoes evaporation. Although evaporation of infiltration water alone was thought to be responsible for secondary gypsum precipitation in vadose caves, our results suggest that condensation can be a major source of water for the formation of gypsum speleothems. The modelled d-excess and Δ 17 O trajectories of water during the evaporative process confirm that the majority of speleothems precipitate from a mixture of condensation and infiltration water under relative humidity of 75–85%, similar to that measured in the cave atmosphere during winter. These findings have important implications for future studies of gypsum speleothems as paleoenvironmental archives.

The dissolution of carbonate host-rock by freshwater in phreatic or vadose conditions is the most common mechanism for the formation of caves; however, circulation of saline solutions through carbonate materials and precipitation of soluble salts may also play an important role. We studied the stable isotope composition (δ18O and δ34S of sulfate, δ18O and δD of structurally-bound gypsum hydration water and 87Sr/86Sr) and salinity of fluid inclusions in gypsum speleothems found in El Orón-Arco Cave (Cartagena, SE Spain). We suggest that physical weathering of carbonate host-rock was driven by precipitation of soluble sea-salts (mostly gypsum and halite), and this process controlled the recent geomorphological evolution of the cave. The Triassic carbonate host-rock shows clear evidence for salt weathering, including gypsum/halite infillings in cracks of the bedrock, mechanical spalling of the carbonate, and detachment of rock fragments that lead to the formation cave voids and in-situ accumulations of piles of unsorted rubble. Sulfur and oxygen isotopes of gypsum sulfate (3.0‰, Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

The Gruta de las Maravillas cave is located at the WNW side of the Cerro del Castillo hill in Aracena (Huelva, SW Spain). The cavity is hosted within marbles included in a strip of high-grade metamorphic rocks belonging to the so-called Aracena Massif in the southernmost Ossa-Morena Zone. The hill is made up of granodiorites, marbles, quartzites, and gneisses, with the foliation trending N110°E and dipping roughly 60–80° towards NE. The marbles appear highly deformed in ductile conditions, with isoclinal folds of different sizes, boudins, porphyroblasts with sigmoidal morphology, and left-lateral S-C shear fabrics. Close to the granodiorite contact, the marbles include a thin band of disseminated and massive pyrite, partially transformed to Fe-oxides. Analysis of the brittle deformation and the associated paleostresses indicates a NE–SW oriented maximum compression, probably related to the latest Variscan collisional tectonics (300 Ma; Late Carboniferous). The Gruta de las Maravillas is divided into three main levels (located at ~ 650, ~ 665 and ~ 685 m a.s.l.), the dissolution having progressed from top to bottom in different stages of stability of the water table. The initial dissolution phases were probably favoured by the presence of pyrite in the host rock, which, in turn, would have caused acidification of the circulating water. Favouring this hypothesis, a thin layer of Fe-oxides, locally including gypsum, covers some parts of the cave walls. The morphology and structure of the cavity result from interaction between the general NNE dipping foliation with sub-perpendicular joints, the pyrite-bearing band in the host marbles, and the descending water table.

The detection of caves developed in gypsum and marls through geophysical methods is tested in the gypsum karst of Sorbas (SE Spain). We applied microgravity and electrical resistivity tomography (ERT) in the Covadura cave system, which features a large variety of shapes developed in a multilayer structure. The response of caves in different conditions of host rocks and cave dimensions is analysed by means of synthetic models. Gravity studies require very accurate conditions in data acquisition and processing to highlight the associated minima, given the low density contrast between caves and gypsum or marl host rock. Different microgravity station spacing was tested to find the best configuration for the detection of such caves. The suitability of ERT under different conditions of soil humidity is discussed in conjunction with the low resistivity contrast between gypsum bedrock and cave conduits. After measuring 2D ERT parallel profiles coincident in space, yet in wet versus dry soil conditions, the results were compared and it was determined that the ERT profiles measured under wet soil conditions are better than in dry ones for cave detection. A 3D model was drawn up for the two different humidity conditions to obtain the fitted morphology of the cave. The best results for cave detection are obtained when combining gravity and ERT in wet conditions, as they provide for a higher contrast in physical properties and an optimal setting for instrumental measurements.

This project was supported by Centro de Investigación en Ciencias Geológicas of Universidad de Costa Rica (830-B7-A00) and the Costa Rican Department of Science and Technology (MICITT) fund FI-160B-14 to Andrés Ulloa Carmiol. The caves of the Irazú volcano (Costa Rica), became accessible after the partial collapse of the NW sector of the Irazú volcano in 1994, offering the opportunity to investigate active minerogenetic processes in volcanic cave environments. We performed a detailed mineralogical and geochemical study of speleothems in the caves Cueva los Minerales and Cueva Los Mucolitos, both located in the northwest foothills of the main crater. Mineralogical analyses included X-ray diffraction (XRD) and Raman spectroscopy, while geochemical characterization used Energy Dispersive X-ray spectroscopy (EDX) coupled to Scanning Electron Microscopy (SEM). In addition, measurements of environmental parameters in the caves, cave drip water and compilation of geochemical analyses of the Irazú volcanic lake (~150 m above the cave level) and fumarole analyses were conducted between 1991 and 2014. We identified forty-eight different mineral phases, mostly rare hydrated sulfates of the alunite, halotrichite, copiapite, kieserite and rozenite groups, thirteen of which are described here as cave minerals for the first time. This includes the first occurrence in cave environments of aplowite, bieberite, boyleite, dietrichite, ferricopiapite, ferrinatrite, lausenite, lishizhenite, magnesiocopiapite, marinellite, pentahydrite, szomolnokite, and wupatkiite. The presence of other new cave minerals such as tolbachite, mercallite, rhomboclase, cyanochroite, and retgersite, is likely but could not be confirmed by various mineralogical techniques. Uplifting of sulfurous gases, water seepage from the Irazú volcanic lake and hydrothermal interactions with the volcanic host rock are responsible for such extreme mineralogical diversity. These findings make the caves of the Irazú volcano a world-type- reference locality for investigations on the formation and assemblage of sulfate minerals and the biogeochemical cycle of sulfur, with potential implications for Astrobiology and Planetary science. Publisher PDF

Fascinating and fragile environments as are the underground estuaries, need to be studied, understood and protected for present and future generations. Even if wide and abundant bibliography related to tides and their behaviour with respect to the external estuaries is available, none dealed with the estuary caves and the related hydrogeology. This paper aims to partially fill this gap presenting a preliminary study done at the Puerto Princesa Underground River (PPUR), in the Palawan Island (Philippines). The data was collected during the last expedition (November 2016) organised by La Venta, in which some of the authors took part. During the survey, the cave has been instrumented with in continuous diver data-logger devices (CTD) recording temperature (T), electrical conductivity (EC) and water level fluctuations. Longitudinal and vertical water hydrogeological profiles of the cave were realised with the aim of understanding the dynamics of the waters during different hydrogeological regimes in combination with salt water intrusion. In addition, a bathymetric profile was done to better identify the point where to realise the vertical logs. A significant rainstorm occurred during the expedition, lasting for approximately 12 hours resulting in 80 mm of rain, and its effects gave the researchers the opportunity to analyse the hydrodynamics of the flowing waters during a flood. In normal flow conditions, the longitudinal logs highlighted the presence of freshwater inlets and the vertical logs testified to a clear stratification of the waters (freshwaters at the surface and brackish waters at the bottom). During floods, the EC and T data showed evidence of a fast substitution of the resident waters. Key words: anchialine caves, sea water intrusion, hydrodynamics, karst springs, PPUR, Philippines. Ucinek mocnega naliva na hidrodinamiko podzemske reke Puerto princese (Palawan, Filipini) Ocarljivo in obcutljivo okolje, kot so podzemni estuariji, je treba preucevati, razumeti in zascititi za sedanje in prihodnje generacije. Cetudi imamo na voljo siroko in bogato bibliografijo o plimovanju in delovanju plimovanja v zunanjih estuarijih, nobeno delo ne obravnava estuarskih jam in s tem povezane hidrogeologije. Namen tega clanka je delno zapolniti to vrzel in predstaviti predhodno studijo na podzemni reki Puerto Princesa (PPUR) na otoku Palawan (Filipini). Podatki so bili zbrani med zadnjo ekspedicijo (novembra 2016), ki jo je organizirala La Venta, v kateri so sodelovali tudi nekateri avtorji. V raziskavi je bila jama opremljena z zveznimi merilci (CTD) temperature (T), elektricne prevodnosti (EC) in nihanja nivojev vode. Vzdolžni in navpicni hidrogeoloski vodni profili jame so bili izmerjeni, da bi razumeli dinamiko voda med razlicnimi hidrogeoloskimi nivoji in med vdori morske vode. Poleg tega je bil opravljen tudi batimetricni profil, da bi lažje dolocili, kje izvesti navpicne meritve. Med ekspedicijo se je zgodil mocan naliv, ki je trajal približno 12 ur, padlo je 80 mm dežja, njegov ucinek pa je raziskovalcem omogocil analizo hidrodinamike tekocih voda med poplavo. V obicajnih vodostajih so vzdolžne meritve pokazale na dotoke sveže vode, vertikalne meritve pa so pokazale jasno stratifikacijo lastnosti vode (sveža voda na povrsini in brakicna voda na dnu). Med poplavami so podatki EC in T potrdili hitro zamenjavo vode. Kljucne besede: anhialine jame, vdor morske vode, hidrodinamika, kraski izviri, PPUR, Filipini.

The hydrothermal caves linked to active faulting can potentially harbour subterranean atmospheres with a distinctive gaseous composition with deep endogenous gases, such as carbon dioxide (CO2) and methane (CH4). In this study, we provide insight into the sourcing, mixing, and biogeochemical processes involved in the dynamic of deep endogenous gas formation in an exceptionally dynamic hypogenic karst system (Vapour Cave, southern Spain) associated with active faulting. The cave environment is characterized by a prevailing combination of rising warm air with large CO2 outgassing (>1%) and highly diluted CH4 with an endogenous origin. The δ13CCO2 data, which ranges from −4.5 to −7.5‰, point to a mantle-rooted CO2 that is likely generated by the thermal decarbonation of underlying marine carbonates, combined with degassing from CO2-rich groundwater. A pooled analysis of δ13CCO2 data from exterior, cave, and soil indicates that the upwelling of geogenic CO2 has a clear influence on soil air, which further suggests a potential for the release of CO2 along fractured carbonates. CH4 molar fractions and their δD and δ13C values (ranging from −77 to −48‰ and from −52 to −30‰, respectively) suggest that the methane reaching Vapour Cave is the remnant of a larger source of CH4, which was likely generated by microbial reduction of carbonates. This CH4 has been affected by a postgenetic microbial oxidation, such that the gas samples have changed in both molecular and isotopic composition after formation and during migration through the cave environment. Yet, in the deepest cave locations (i.e., 30 m below the surface), measured concentration values of deep endogenous CH4 are higher than in atmospheric with lighter δ13C values with respect to those found in the local atmosphere, which indicates that Vapour Cave may occasionally act as a net source of CH4 to the open atmosphere., This work was supported by the Spanish Ministry of Economy and Competitiveness [projects: GEIs-SUB (CGL2016-78318-C2-1R and CGL2016-78318-C2-2R AEI/FEDER/UE) and CGL2017-83931-C3-2-P].

Speleothems are usually composed of thin layers of calcite (or aragonite). However, cemented detrital materials interlayered between laminae of speleothemic carbonate have been also observed in many caves. Flowstones comprising discontinuous carbonate layers form due to flowing water films, while flood events introduce fluviokarstic sediments in caves that, on occasion, are recorded as clayey layers inside flowstones and stalagmites. This record provides a potential means of understanding the frequency of palaeofloods using cave records. In this work, we investigate the origin of this type of detrital deposit in El Soplao Cave (Northern Spain). The age of the lowest aragonite layer of a flowstone reveals that the earliest flood period occurred before 500 ka, though most of the flowstone formed between 422 +69/-43 ka and 400 +66/-42 ka. This suggests that the cave was periodically affected by palaeoflood events that introduced detrital sediments from the surface as a result of occasional extreme rainfall events, especially at around 400 ka. The mineralogical data enable an evolutionary model for this flowstone to be generated based on the alternation of flood events with laminar flows and carbonate layers precipitation that can be extrapolated to other caves in which detrital sediments inside speleothems have been found. Copyright © 2014 John Wiley & Sons, Ltd.

The “espada” speleothems of Cueva de las Espadas (Naica Mine, Chihuahua, Mexico) comprise a high-purity selenite core overlain by successive deposits of calcite, gypsum and aragonite. Gypsum precipitated under water from a hydrothermal solution (~ 58°C) when the water table was above the cave level ca. 57 ka, during the last glaciation, and some intervals during deglaciation and the Holocene. Aragonite was deposited at lower temperatures (~ 26°C) in a perched lake occupying the cave bottom, when the water table dropped below the cave level during brief dry intervals during deglaciation and the early Holocene. The isotopic composition of gypsum water of crystallization shows that the deglaciation–Holocene aquifer water was enriched in deuterium by 12.8–8.7‰ relative to water from the last glaciation. This is attributed to an increased relative moisture contribution from the Gulf of Mexico during deglaciation and the Holocene compared to the last glaciation. This indicates that drier conditions occurred in the Naica area during the Holocene than around 57 ka. Furthermore, trace element analyses of gypsum served to deduce the circulation regime of the Naica aquifer during the past 60,000 yr, and also suggest that higher aquifer recharge occurred during the last glaciation.

The karst of Sorbas (SE Spain) is one of the most important gypsum areas worldwide. Its underground karst network comprises over 100 km of cave passages. Rounded smooth forms, condensation cupola and pendant-like features appear on the ceiling of the shallower passages as a result of gypsum dissolution by condensation water. Meanwhile, gypsum speleothems formed by capillarity, evaporation and aerosol deposition such as coralloids, gypsum crusts and rims are frequently observed closer to the passage floors. The role of condensation–dissolution mechanisms in the evolution of geomorphological features observed in the upper cave levels has been studied by means of long-term micro-erosion meter (MEM) measurements, direct collection and analysis of condensation waters, and micrometeorological monitoring. Monitoring of erosion at different heights on gypsum walls of the Cueva del Agua reveals that the gypsum surface retreated up to 0.033 mm yr− 1 in MEM stations located in the higher parts of the cave walls. The surface retreat was negligible at the lowest sites, suggesting higher dissolution rates close to the cave ceiling, where warmer and moister air flows. Monitoring of microclimatic parameters and direct measurements of condensation water were performed in the Covadura Cave system in order to estimate seasonal patterns of condensation. Direct measurements of condensation water dripping from a metal plate placed in the central part of the El Bosque Gallery of Covadura Cave indicate that condensation takes place mainly between July and November in coincidence with rainless periods. The estimated gypsum surface lowering due to this condensation water is 0.0026 mm yr− 1. Microclimatic monitoring in the same area shows differences in air temperature and humidity of the lower parts of the galleries (colder and drier) with respect to the cave ceiling (warmer and wetter). This thermal sedimentation controls the intensity of the condensation–evaporation mechanisms at different heights in the cave.

Signs of hypogenic speleogenesis have been detected in a number of caves of the Murcia Region (SE Spain), in some cases revealing active speleogenetic mechanisms rarely observed in hypogene cavities elsewhere in the world. Here, we investigate the hypogenic morphologies and speleothems of four caves in this region, namely Sima de la Higuera, Sima Destapada, Cueva del Agua and Cueva del Puerto. Also, other ten caves showing evidence for hypogenic speleogenesis has been preliminary described. Processes related to ancient and current hydrothermal activity, the discordance of permeability structures in the adjacent beds and the spatial arrangement of the regional hydrogeology have given rise to maze patterns and typical subaqueous hypogenic morphologies. These include spongework mazes, rising wall channels and shafts, feeders, bubble trails, solution pockets, megascallops and rising of chains cupolas, among others. Carbonic acid speleogenesis is responsible for the formation of most of these cave features; however, evidence of sulfuric acid speleogenesis (SAS) has been observed in Cueva del Puerto and Sima del Pulpo, which host massive secondary gypsum deposits. Speleothems typically linked to hydrothermal water upwelling and CO2 degassing close to the water table are present in most of these cavities, including folia, calcite spar crystals, cave clouds, calcite rafts deposits and several types of cave raft cones. The wide variety of hypogenic speleogenesis indicators and speleothems whose genesis is unconnected to meteoric water seepage reveals that the hydrothermal field of the Murcia Region hosts one of the densest active hypogenic subterranean networks in the world.

In the present paper, we describe the genetic mechanism that causes the precipitation of raft cones in caves. These speleothems usually form in a hydrothermal and epiphreatic environment where dripwater, dripping repeatedly over the same spot, sinks calcite rafts that were floating on the water surface of a cave pool. In particular, the paper describes a new variety of raft cones that were recently discovered in the Paradise Chamber of the Sima de la Higuera Cave (Murcia, south-eastern Spain) based on their morphological and morphometric characteristics. These speleothems, dubbed ‘double-tower cones’, have a notch in the middle and look like two cones, one superimposed over the other. The genetic mechanism that gave rise to the double-tower cones must include an intermediate stage of rapid calcite raft precipitation, caused by a drop in the water table and by changes in cave ventilation leading to greater carbon dioxide (CO2) degassing and evaporation over the surface of the thermal lake where these speleothems formed. Calcite rafts were deposited in Paradise Chamber, completely covering many of the cones. Later, conditions for slower calcite raft precipitation were restored and some of the cones continued to grow at the same points. When the water table finally fell below the level of Paradise Chamber, the tower cones became exposed, as the incongruent deposits of calcite rafts were dissolved and mobilized to lower cave levels. Copyright © 2013 John Wiley & Sons, Ltd.

This paper examines the greyish-blue deposits that were recently discovered in the lower levels of the Sima de la Higuera Cave (Murcia, SE Spain) which occur as patinas over the walls and ceilings, as well as coating boxwork formations. Their mineralogy was determined using XRD and micro-Raman spectroscopy, while EDX microanalysis was used to determine their elemental composition. The mineralogical analyses revealed the presence of Mn oxides (todorokite and pyrolusite) and Fe with a low degree of crystallinity, whereas EDX microprobe showed elevated concentrations of Mn (38.2 wt.%), Fe (15.2 wt.%) and Pb (8.1 wt.%). The ferromanganese oxyhydroxides occur as botryoidal aggregates overlying blades of calcite that have a visibly sugary texture. The speleogenetic model proposed describes (1) an initial phase of precipitation of hydrothermal calcite veins (of hypogenic origin) within the fissures of the host rock under phreatic conditions and (2) a subsequent vadose phase involving preferential corrosion of the carbonate host rock caused by lowering of the pH resulting from CO 2 diffusion in condensed water and oxidation of Fe and Mn under aerobic conditions, probably mediated by microorganisms. It is this later phase that gave rise to the boxwork . The boxwork of the Sima de la Higuera Cave is a singular example of a formation that is generated by dissolution–corrosion of the rock due to acidification caused by oxidation of iron and manganese.

During a trip to the Hall of the White Giant, Carlsbad Caverns (NM, USA) cigar-shaped vertically upward developing holes were observed on the ceiling at different heights of the passages. They have a circular cross-section with diameters of 1 to some centimetres and taper out towards their upper end. Their walls are smooth and their bottom edges are sharp, while their length can reach several decimetres. Sometimes gypsum can be found inside. They often occur randomly distributed in groups and their development is not necessarily controlled by fractures or other bedrock structures. We name these peculiar karren-like cave microforms “zenithal ceiling tube-holes” because of their origin by H 2 S environment corrosion processes and their vertical (zenithal) upward growth in ceilings. A comparison is made between zenithal ceiling tube-holes and other karstic or non karstic similar forms such as bell holes, oxidation vents, snailholes, Korrosionskolke (mixture-solution hollows) or pockets, rohrenkarren , light-oriented photokarren, borings of (often marine) organisms and negative stalactites. Zenithal ceiling tube-holes are created by the corrosive effect of sulphuric acid. H 2 S(g) dissolves in water giving rise to widespread sulphuric acid corrosion. When H 2 S bubbles are trapped underneath overhanging surfaces or ceilings and water level rises steadily the corrosive effect is concentrated vertically upwards, drilling vertical holes that can also completely pass overhanging rock ledges.

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 first cavity in which the lowering of temperature induced by mine ventilation caused condensation over crystals’ surface since 2005. The consequent dissolution of the gypsum crystals and subsequent condensed water evaporation lead to the deposition of several new minerals, among which some highly soluble Mg/Na compounds (bloedite, epsomite, halite, hexahydrite, kieserite, starkeyite). The single available source of Mg and Na ions in this minerogenetic environment is represented by the huge fluid inclusions widespread within the crystals. The condensation occurs mainly along the widened principal exfoliation (010) planes, and allows to an easy and fast opening of the fluid inclusions that consequently drip Mg-rich fluids stored inside them. Finally the evaporation of the relatively small volumes of involved water allows to the development of the high soluble Mg and Na compounds.

Karst caves exhibit a wide range of hydrological and hydrochemical responses to infiltration events, due to their physical heterogeneity space and dynamic variability over time, and due to non-Gaussian inputs (rain) and outputs (discharge). This paper reviews different approaches of studying seepage water in caves, in order to understand the infiltration regimen in the non-saturated zone of karst areas. As an illustration, we describe a four-year study of the active carbonate-water system the Cueva del Agua (Granada, southern Spain) that automatically logs the discharge from a stalactite. The results indicate that: (1) the drip water regime is not seasonal, but is linked instead to slow infiltration. Sudden changes in drip water regime occur due to infiltration along preferential flow paths and the draining of water of supersaturated water from reserves in the microfissure and pore system; (2) the drip rate is not linear over time. When dripping is constant, barometric oscillation of the air is the principal factor causing a chaotic a drip flow regime. Over a short period of two to three days, a mean variation in air pressure inside the cave of 10 (±3.7) mbar causes a oscillation the drip rate of 0.5 (±0.2) mm/h. The increase air translates into an the relative thickness of the gaseous phase of the drip water at the cost of the aqueous phase, so leading to a reduction the drip rate from the stalactite.

On 28th September 2012, more than 150 mm rain fell in just two hours in some points of southeastern Spain, triggering intense flash floods that resulted in the death of ten people and widespread material damage. In the gypsum karst of Sorbas, rainfall intensity reached 33 mm/h. Air temperature monitoring in different levels of Covadura Cave, down to 85 m depth, enabled the effect of this extreme episode on the cave microclimate to be evaluated in real time. The cave air temperature increased by between 0.9 and 4.1 °C as a result of water flow into the cavity and intense mixing of air masses, in addition to the displacement of deeper air masses toward shallower levels produced by fast recharge of the surrounding karst aquifer. The lag between peak rainfall intensity and the highest cave air temperature was 5–6 h, indicating the response time of the karst to this rainfall event. No trends with depth were observed, suggesting that water not only flowed in through the main cave entrance but also through secondary accesses and fractures. Furthermore, the size of the cave passages and the intensity of air turbulence generated by waterfalls in the cave played an important role in producing these temperature differences. Even though the rainfall event lasted 10 h, cave air temperature did not return to pre-flash flood values until more than 20 days later. This indicates that, while waterflow through the cave might stop a few hours after the rainfall event, cave air temperature can be affected over a longer period. This can be explained by slow groundwater level decreasing of the surrounding karst aquifer and latent heat liberation produced by moisture condensation on the cave walls. Our results show how continuous monitoring of air temperature in caves can be a useful tool for evaluating the short-term effects of flash floods in subterranean karst systems., Financial support was made available through funds from the Water Resources and Environmental Geology Research Group (University of Almería) and the ‘‘GLOCHARID’’ Project (852/2009/M/00) of the Junta de Andalucía Regional Government. Funding was also provided by the People Programme (Marie Curie Actions – Intra-European Fellowships, call 2013) of the European Union’s Seventh Framework Programme (FP7/2007-2013) under REA grant agreement no. 624204 to Dr. Fernández-Cortés.

7 páginas.-- 3 figuras.-- 21 referencias.-- Comunicación oral presentada en el 7th International Symposium of Vulcan speleology At Ocean View, Big Island, Hawaii (USA) February 6-12, (2016), Different types of hard and soft speleothems (stalactites, stalagmites, columns, crusts, flowstones, micro-gours and botryoidal coralloids) have been observed throughout lava tubes in the Galapagos archipelago, Ecuador. Three lava tubes were studied in this work: Gallardo and Royal Palm volcanic caves (Santa Cruz Island) and Sucre Cave (Isabela Island). The studied speleothems were mainly formed by opal, calcite and clay minerals, including plagioclase and pyroxenes from the basaltic host rock. Rarely, iron oxides, gypsum were found in some speleothems, which were interpreted as alteration products of the primary volcanic materials. Field emission scanning electron microscopy revealed abundant filamentous, The sampling and analyses presented in this work were supported by the project PC-65-14 “Genesis y Mineralogía de los espeleotemas secundarios de los tubos volcánicos de las Islas Galápagos” from the Ministry of Environment of Ecuador, and the projects CICYT AYA2011-30291-C02-02, CGL2013-41674-P and ESP2013-48427-C3-2-R of MINECO from the Spanish Ministry of Economy and Competitiveness, and FEDER funds. A.Z. Miller acknowledges the support from the Marie Curie Intra-European Fellowship of the European Commission’s 7th Framework Programme (PIEF-GA-2012-328689)

A study of drip water from a stalactite in the Cueva del Agua (Granada, southern Spain) over four hydrological years has enabled a detailed characterization of infiltration through the non-saturated zone of this cave. The most significant aspects are: (1) The drip water regime is not seasonal, but is linked instead to slow infiltration. Sudden changes in the drip water regime are detected, due to infiltration along the preferential flow paths and the draining of water of supersaturated water reserves from the microfissure and pore system. (2) The accumulation of excess rain in the unsaturated zone dislodges the reserve of supersaturated water from the matrix of microfissures and pores, giving rise to an average increase in drip intensity of 2·2 ± 0·5 mm h−1 and 37 ± 13 µS cm−1 in the electrical conductivity of the water. (3) Time-series analysis of the drip water demonstrates a lack of linearity over time of the drip rate, indicating a chaotic regime. (4) When the dripping is constant, barometric oscillation of the air is the principal factor that causes the lack of linearity in the drip flow. In this way, over an average of 2–3 days, a mean variation of the air pressure inside the cave of 10 ± 3·7 mbar causes a mean oscillation in the drip rate of 0·5 ± 0·2 mm h−1. This increase in air pressure is translated as an increase in the relative thickness of the gaseous phase of the drip water at the cost of the aqueous phase, so reducing the drip intensity of the stalactite. Copyright © 2006 John Wiley & Sons, Ltd.

Wetest the capabilities of in situ Raman spectroscopy for non-destructive analysis of degradation processes in invaluable masterpieces, as well as for the characterization of minerals and prehistoric rock-art in caves. To this end, we have studied the mechanism of decay suffered by the 15th-century limestone sculptures that decorate the retro-choir of Burgos Cathedral (N Spain). In situ Raman probe detected hydrated sulfate and nitrateminerals on the sculptures, which are responsible for the decay of the original limestone. In addition, in situ Raman analyses were performed on unique speleothems in El Soplao Cave (Cantabria, N Spain) and in the Gruta de las Maravillas (Aracena, SWSpain). Unusual cavemineralswere detected in El Soplao Cave, such as hydromagnesite (Mg5(CO3)4(OH)2·4H2O), as well as ferromanganese oxides in the black biogenic speleothems recently discovered in this cavern. In the Gruta de las Maravillas, gypsum (CaSO4·2H2O) was identified for the first time, as part of the oldest cave materials, so providing additional evidence of hypogenic mechanisms that occurred in this cave during earlier stages of its formation. Finally, we present preliminary analyses of several cave paintings in the renowned “Polychrome Hall” of Altamira Cave (Cantabria, N. Spain). Hematite (Fe2O3) is the most abundant mineral phase, which provides the characteristic ochre-reddish color to the Altamira bison and deer paintings. Thus, portable Raman spectroscopy is demonstrated to be an analytical technique compatible with preserving our cultural and natural heritage, since the analysis does not require physical contact between the Raman head and the analyzed items.

2 páginas.-- 2 figuras, Coralloid-type speleothems were found in Ana Heva lava tube from Easter Island (Chile). The ceiling of the lava tube presents light to dark brown speleothems with globular coral-like shape. To appraise their internal structure and composition, optical microscopy (OM) of cross-sections, field emission scanning electron microscopy with energy dispersive X-ray spectroscopy (FESEM-EDS) and X-Ray micro-computed tomography ( CT) were performed. The latter is a non-destructive method (NDM), performed to assess physical and compositional heterogeneities of the coralloids. The internal structure of these speleothems comprises a succession of thin layers, ranging from white to brown, with vitreous to resinous luster (Fig. 1A). According to their color and texture, four major layers are easily distinguishable, from the surface to their inner part: a superficial dark brown to black coating, with approximately 0.1 mm thick (L1); a 0.1-1 mm thick semi-transparent grayish layer (L2); a 0.1-1 mm thick white layer (L3), and a heterogeneous honey brown layer, with 1-5 mm thick and shades ranging from yellowish to honey brown (L4). FESEM-EDS microanalyses performed on the internal layers of longitudinally cut coralloid samples (Fig. 1B) showed systematic differences in chemical composition of the different color inner layers. In general, they contain variable proportions of Si, Mg and Ca (Fig. 1C-G). According to a previous study [1], the thin dark brown to black coating of the coralloid surfaces is probably derived from the weathering of the overlying volcanic rock and microbial activity [1]. The semi-transparent grayish layer (L2) is composed of low crystalline silica (opal-A), whereas the whitish layers (L3) are calcium carbonate (calcite). In contrast, the honey-brown layers (L4) present an unusual composition characterized by high levels of Mg, corresponding to an amorphous Mg hydrate silicate. Significant content of organic carbon was also found in these layers [1]. The CT study allowed us to confirm the existence of internal zoning in the studied coralloids (Fig. 2), and between them and the basaltic substrate. The brighter domains in the reconstructed images (Fig. 2D,E) correspond to the vacuolar basaltic. The other opaque domains, comprising thin spheroidal precipitates or dispersed spots within the coralloids (Fig. 2F-I), are calcium rich phases. According to mineralogical data and FESEM-EDS analysis, the inner/older spots correspond to apatite and the outer/more recent spots correspond to calcite. In contrast, the Si, Mg and C enriched domains are more transparent to X-ray radiation, combining at least two main phases (siliceous and magnesium silicate compounds). The proposed methodology was considered adequate for studying coralloid samples, by combining a NDM (μCT) with other microanalytical techniques. Investigations of speleothems using the potentialities of μCT provide general morphological and compositional information, suggesting the best approach for selecting and sectioning the samples. The FESEM-EDS provides characteristic information on the morphological, mineral and chemical composition., The authors acknowledge FCT for PEst-OE/CTE/UI0098/2011, AZM (SFRH/BPD/63836/2009) grant, and Spanish Ministry of Science and Innovation (Project CGL2011-2569) and CSIC 210230E125.

A comprehensive environmental monitoring program was conducted in the Ojo Guareña cave system (Spain), one of the longest cave systems in Europe, to assess the magnitude of the spatiotemporal changes in carbon dioxide gas (CO2) in the cave–soil–atmosphere profile. The key climate-driven processes involved in gas exchange, primarily gas diffusion and cave ventilation due to advective forces, were characterized. The spatial distributions of both processes were described through measurements of CO2 and its carbon isotopic signal (δ13C[CO2]) from exterior, soil and cave air samples analyzed by cavity ring-down spectroscopy (CRDS). The trigger mechanisms of air advection (temperature or air density differences or barometric imbalances) were controlled by continuous logging systems. Radon monitoring was also used to characterize the changing airflow that results in a predictable seasonal or daily pattern of CO2 concentrations and its carbon isotopic signal. Large daily oscillations of CO2 levels, ranging from 680 to 1900 ppm day−1 on average, were registered during the daily oscillations of the exterior air temperature around the cave air temperature. These daily variations in CO2 concentration were unobservable once the outside air temperature was continuously below the cave temperature and a prevailing advective-renewal of cave air was established, such that the daily-averaged concentrations of CO2 reached minimum values close to atmospheric background. The daily pulses of CO2 and other tracer gases such as radon (222Rn) were smoothed in the inner cave locations, where fluctuation of both gases was primarily correlated with medium-term changes in air pressure. A pooled analysis of these data provided evidence that atmospheric air that is inhaled into dynamically ventilated caves can then return to the lower troposphere as CO2-rich cave air., This research was funded by the Agreement between Fundación Patrimonio Natural (Regional Government of Castilla y León) and CSIC and by the Spanish Ministry of Economy and Competitiveness (MINECO) project CGL2013-43324-R and in collaboration with project CGL2011-25162-BTE., Funding was also provided by the People Programme (Marie Curie Actions—Intra-European Fellowships, call 2013) of the European Union’s Seventh Framework Programme (FP7/2007–2013) under REA grant agreement no. 624204, and the MINECO programme Torres Quevedo (PTQ 13-06296 and PTQ 12-05601).

The discovery of the giant Geode of Pulpi (Almeria, Spain) was considered as an important highlight in the geological heritage of Spain. Projects developed for their conservation were immediately initiated with legal figures of protection and tourist projects. The Geode has a tourist interest, which must be tempered by environmental restrictions limiting the public visits. First results demonstrate that a continuous visit of two or three people for more than 10 min provokes the appearance of condensation and risks corrosion of the gypsum crystals. In addition, the electron microprobe analyses confirms (1) the hydrothermal phases of iron–manganese in carbonated host rock; (2) the presence of sulphides with Fe–Zn–Pb–Ag–Sb–Cu–Hg–As–Te–Se; and (3) Ba, Ca, and Sr sulphates with mercury traces. The present proposal to label the geode and the mining environment as geological-natural heritage is feasible, although any tourist adaptation must not permit visits to the geode indoor and Hg levels must be controlled.

Unusual orange ochre crusts were recently discovered in Crovassa Ricchi in Argento Cave (San Giovanni Mine, SW Sardinia). These speleothems appear covering the cave walls on hydrothermal calcite spars as well as filling widened spaces between calcite crystals. Planar crusts display geometrical forms following the boundaries between the calcite spars. EDX-SEM microanalyses reveal that these deposits comprise substances of Fe, Mn, Pb, Zn and O that occur as solid inclusions in pits on the surface of altered calcite microcrystals. Micro-Raman spectroscopy analyses suggest the presence of calcite and ferromanganese oxides with a low degree of crystallinity. The genetic mechanism proposed for these speleothems describes an initial stage of precipitation of euhedral calcite crystals from warm water under subaqueous conditions. The crystal surfaces were eroded and corroded by colder aggressive water that smoothed the surfaces of the crystals and slightly widened the spaces between calcite spars. Metal-rich mud coming from alteration of bedrock and ore bodies filled the cave, also penetrating along the spaces between the calcite spars. When the water table fell below the cave level, part of the sediments was eroded but the cave walls remained covered with metal-rich clayey sediments. Under aerobic conditions, metals - which were reduced in previous stages - oxidized to oxides, lowering the pH and thus the crystal surface and the calcite planes between the spars were corroded. Subsequently, the polymetallic crusts became harder through evaporation within the cave, "fossilizing" the products of this process within the planes between spars. Finally, the exposed calcite surfaces continued to be altered due to CO2 diffusion into condensation water, while the boundaries between crystals were preserved against corrosion thanks to the crust coating. As a result, the external crystal edges protrude by several centimeters from the current cave wall, while the crystal surfaces are depressed, giving rise to calcite "ghosts". © 2013 Elsevier B.V. All rights reserved.

A comprehensive environmental monitoring programme has been recently launched in Ojo Guareña cave system (Burgos, Spain), one of the longest caves in Europe, aimed to assess the magnitude of the spatiotemporal changes of CO2 (g), on daily and synoptic timescales in the cave–soil–atmosphere profile. CO2 concentration of cave air is usually close to atmospheric background but huge daily oscillations of CO2 levels, ranging 680–1,900 ppm/day on average, have registered during periods when exterior air temperature oscillates every day around cave air temperature. These daily variations of CO2 content are hidden once the air temperature outside is continuously below cave temperature and a prevailing advective-renewal of cave air is established, so that daily-averaged concentrations of CO2 reach minimum values close to 500 ppm. The spatiotemporal pattern of CO2(g) provides evidence that the amounts of carbon that might be sequestered and then emitted (CO2) from subsurface air located in the uppermost part of the vadose zone could be noticeable at local or regional scale by considering long subterranean systems as Ojo Guareña karst.

Among the numerous karstified gypsum outcrops of the Betic Cordillera, in this article we present three extreme examples, with markedly different origins and development: (1) the Antequera gypsum karst, where diapiric phenomena have had a decisive influence on the geomorphological and hydrogeological evolution of the area; (2) the karst in gypsum of Vallada, with its processes of hyperkarstification of gypsum caused by the presence of significant quantities of halite; and (3) the Sorbas gypsum karst, where a complex speleogenetic development is demonstrated by a succession of vadose and phreatic passages within a multilayer aquifer. In these three cases, we have considered the geomorphological evolution of gypsum karst based on hydrogeological information gathered in each of the outcrop areas in a way which integrates both aspects into a more generalized speleogenetic model.

The gypsum karst of Sorbas is one of the most well-known gypsiferous areas in the world from the speleological point of view. The Yesares formation comprises an alternating sequence of gypsum and marly strata deposited during the Messinian salinity crisis. The development of the cave systems is closely linked to this alternation of sediments. The caves have been mainly formed by erosion of the marl units, whilst gypsum dissolution was especially active during the initial stages. On the surface, striking karst landforms are found, such as gypsum tumuli, a great variety of dolines formed by different mechanisms, several types of karren, as well as a 30-m-high gypsum scarp. Proto-conduits on the ceilings of the galleries, as well as some sedimentary features, provide evidence of the initial phreatic speleogenetic phases. In addition, the gypsum caves of Sorbas have a great deal of speleothems, some of them unique worldwide (e.g. gypsum balls, hollow stalagmites, gypsum trees and trays, and deflated stalagmites). The protection of the gypsum karst of Sorbas, due to the wide variety of surface and subsurface geomorphological features, should be considered of top priority for the administration.

The present work deals with the results of long-term micro-erosion measurements in the most important gypsum cave of Spain, the Cueva del Agua (Sorbas, Almeria, SE Spain). Nineteen MEM stations were positioned in 1992 in a wide range of morphological and environmental settings (gypsum floors and walls, carbonate speleothems, dry conduits and vadose passages) inside and outside the cave, on gypsum and carbonate bedrocks and exposed to variable degree of humidity, different air flow and hydrodynamic conditions. Four different sets of stations have been investigated: (1) the main cave entrance (Las Vinicas spring); (2) the main river passage; (3) the abandoned Laboratory tunnel; and (4) the external gypsum surface. Data over a period of about 18 years are available. The average lowering rates vary from 0.014 to 0.016 mm yr− 1 near the main entrance and in the Laboratory tunnel, to 0.022 mm − 1 on gypsum floors and 0.028 mm yr− 1 on carbonate flowstones. The denudation data from the external gypsum stations are quite regular with a rate of 0.170 mm yr− 1. The observations allowed the collecting of important information concerning the feeding of the karst aquifer not only by infiltrating rainwater, but under present climate conditions also by water condensation of moist air flow. This contribution to the overall karst processes in the Cueva del Agua basin represents over 20% of the total chemical dissolution of the karst area and more than 50% of the speleogenetically removed gypsum in the cave system, thus representing all but a secondary role in speleogenesis. Condensation–corrosion is most active along the medium walls, being slower at the roof and almost absent close to the floor. This creates typical corrosion morphologies such as cupola, while gypsum flowers develop where evaporation dominates. This approach also shows quantitatively the morphological implications of condensation–corrosion processes in gypsum karst systems in arid zones, responsible for an average surface lowering of 0.047 mm yr− 1, while mechanical erosion produces a lowering of 0.123 mm yr− 1.

[ES]El reciente descubrimiento de minerales hidratados sobre la superficie de Marte sugiere la presencia de importantes cantidades de agua líquida durante algunas etapas de su historia geológica. A raíz de este hallazgo, los estudios sobre minerales hidratados en ambientes terrestres como potenciales análogos marcianos han adquirido gran relevancia. En el presente trabajo se han estudiado las características mineralógicas y geoquímicas de minerales hidratados procedentes de varias cuevas y minas españolas y de la región minera de Iglesias-Carbonia (Cerdeña, Italia) mediante técnicas espectroscópicas implicadas en misiones de exploración marciana presentes y futuras, con el fin de evaluar su potencial para la detección de este tipo de minerales. Por un lado, se ha utilizado la espectroscopia Raman, que formará parte de la carga científica de la misión ExoMars de la Agencia Espacial Europea. Por otro lado, la espectroscopia de IR, otra de las técnicas involucradas en esta misión de la ESA, así como la espectroscopia LIBS y la combinación de difracción-fluorescencia de rayos X (DRX-FRX), ambas a bordo de la misión MSL de la NASA. Estas técnicas han permitido identificar sulfatos (yeso, epsomita, jarosita y glaucocerinita), silicatos (hemimorfita) y carbonatos (hidrocincita e hidromagnesita), todos ellos minerales hidratados y algunos de los cuales también han sido descritos en Marte. Por otro lado, se han abordado los procesos de formación de estos minerales y las potenciales analogías con la mineralogénesis en Marte. Del conjunto de técnicas empleadas, la combinación Raman-LIBS se perfila como la opción más eficiente para la detección de minerales hidratados en condiciones marcianas., [EN] The recent discovery of hydrated sulfates on the Martian surface suggests that widespread wet conditions were present during its early geological history. Upon this discovery, a growing interest has emerged in the study of this group of minerals from terrestrial environments as potential Martian analogs. Here, we evaluate the potential of various analytical techniques involved in current and future mission to Mars for detecting hydrated minerals from caves and mines of Spain and the mining district of Iglesias-Carbonia (Sardinia, Italy). Minerals were analyzed by Raman spectroscopy, which will be included in the payload of the ESA’s 2018 ExoMars mission. On the other hand, IR spectroscopy, also included in the ExoMars mission, as well as LIBS spectroscopy and a combined XRD-XRF analyzer, both onboard the Curiosity rover of NASA’s MSL mission, were utilized. Hydrated sulfates (gypsum, epsomite, jarosite and glaucocerinite), silicates (hemimorphite) and carbonates (hydrozincite and hydromagnesite) were characterized. Most of these minerals have also been detected on the Martian surface. The mechanisms involved in the genesis of these minerals and the potential analogies with the minerogenesis on Mars are discussed. The Raman-LIBS combination appears to be the most powerful tool for detecting hydrated minerals in Martian conditions. This technology will probably be considered to be onboard of further planetary missions

Although geology was the premier science in the United States (and indeed the world) throughout the nineteenth century (Gates et al., 2002), its popularity andFigure 9.1 Map of the United States showing the locations of National Parks and local sites that are discussed in the text. (A) Arches National Monument; (AF) Agate Fossil Beds National Monument; (B) Badlands National Park; (CL) Crater Lake; (D) Dinosaur National Monument; (DT) Devil’s Tower National Monument; (FB) Fossil Butte National Monument; (FL) Florissant Fossil Beds National Monument; (GC) Grand Canyon National Park; (H) Hagerman Fossil Beds National Monument; (JD) John Day Fossil Beds National Monument; (K) Katmai National Park; (M) Mammoth Caves National Park; (P) Petrified Forest National Monument; (S) Sterling Hill Mine; (SH) Mount Saint Helens National Park; (V) Volcanoes National Monument; (Y) Yosemite National Park; (YS) Yellowstone National Park. Cities (bold letters): A, Atlanta; B, Boston; C, Chicago; D, Dallas; LA, Los Angeles; M, Miami;W,Washington, DC; SF, San Francisco.

The Messinian gypsum of Sorbas is intensively karstified, with hundreds of dolines and numerous, highly unusual exo- and endokarstic forms. Amongst these the tumuli are especially spectacular, as are the large caverns, adorned with numerous speleothems, some of which have not been described anywhere else in the World. The extraction of the gypsum has impacted practically all the elements of the environment (landscape, water, soil, subsoil, flora, fauna, etc.) and, in particular, all of the karstic forms. In addition to endangering the caves and the natural treasures that they contain, it affects the surface waters, markedly modifying the hydrographic network. Groundwaters, which now occur in the bottom of a quarry, are also affected.

In the Dobrich region, with an area of a little over 4000 km2, two important aquifer systems can be differentiated, which we have named the Upper and Deep Aquifers. The hydrodynamic and hydrogeochemical characteristics of these two aquifers are different. Agricultural activities, livestock units, and urban waste waters and solid wastes constitute the principal sources of contamination of the Upper Aquifer. Furthermore, signs of marine intrusion in some coastal zones have been detected. The Deep Aquifer is found to be affected by hydrogeochemical processes related to hydrocarbons that generate elevated concentrations of H2S and NO2 (which may exceed 10 mg 1−1). This aquifer has numerous deep overflowing boreholes that lack appropriate capping, with the consequent loss of resource, draining in the order of 4 m3 s−1 of thermal and sulphurous waters.