Speleothem Surfaces Research Articles

Cave morphology and moonmilk deposits of Ryongmun Cavern, Democratic People’s Republic of Korea: A Study for the Conservation of Natural Heritage

The Ryongmun Cavern, registered on the World Heritage Tentative List, is the largest and most beautiful karst cave on the Korean peninsula. The characteristics of the cave morphology and moonmilk deposits in the Ryongmun Cavern were studied. A cross section of the main direction of the cave shows that the Ryongmun Cavern is made up mainly of four strata and this caused 4 stages of decline in underground waterline in the course of cave formation. The cave is mainly characterized by NW–SE-trending, NWW–SEE-trending and NNE– SSW-trending passages. The horizontal passages usually have large and wide spaces, whereas the inclined ones are relatively small and narrow. The cave minerals in the Ryongmun Cavern are mainly calcite and aragonite. In the cave, stalactites, stalagmites, limestone columns, cave pearls, etc. Are calcite; and, anthodites are aragonite. In the cave, speleothems display a wonderful underground landscape in harmony with the cave bedrock and groundwater (streams, waterfalls and ponds). The main scenes of the underground karst landscape in the cave are stalactites, stalagmites, limestone columns, stone waterfalls anthodites, underground waterfalls, and underground ponds.The deposits that have been formed recently on the surface of speleothems and walls in the cave are mainly moonmilk composed of hydromagnesite (Mg5(CO3)4(OH)2•4H2O) with an average particle size of 0.55 μm and chemical composition of MgO–29.43% and CaO–6.28%. The moonmilk is present in a white, fine powder form, a hand-rubbed smooth, and a moisture content of 42.0%. Also, the pH is 10.09, which is alkaline. In the Ryongmun Cavern, moonmilk was formed at sites with very low supply of karst water and relatively high wind speeds. The unique underground karst features provide sufficient evidence for geoheritage value of the cave and the characteristics of moonmilk provide a significant implication for management and preservation of the cave environment.

Seasonal variation in airborne microbial communities of the Akiyoshido Cave: Lampenflora dispersed by phototrophic bioaerosols

Lampenflora, such as phototrophic microorganisms, multiply on speleothem surfaces under the show-cave lighting, causing deterioration of the natural and cultural heritages of the caves. Speleothems change color from white to green through microbial photosynthesis and are destroyed by microbial metabolisms. Aerosol transmission are suspected to disperses photosynthetic microorganisms. However, the mechanism underlying the process remains unclear, because the complexity of air ventilation affects the cave atmosphere. In the present study, we collected aerosol samples from the Akiyoshido Cave, which is a special natural monument in Japan and possesses various types of speleothems, to analyze microbial concentrations and communities in the cave atmosphere. Under a fluorescence microscope, phototrophic and heterotrophic microorganisms were observed in the aerosols with in the cave. The aerosol concentrations showed seasonal changes depending on air-flow variations in cave ventilation. High-throughput DNA sequencing targeting 16S rRNA genes revealed that the airborne bacterial communities inside the cave were dominated by members of the phyla Actinomycetota, Bacillota, and Pseudomonadota, originating from the external terrestrial, phyllosphere or freshwater environments, as well as its interior (guano). Cyanobacteria showed small relative abundances (from 1.0 to 10%) randomly in the aerosol samples at several locations in the cave, suggesting that the lampenflora-derived cyanobacteria were dispersed throughout the cave by the ventilation. Additionally, phototrophic microorganisms closely related to the relatives of the genera Leptolyngbya, Calothrix, and Chroococcidiopsis from the phylum Cyanobacteria were isolated from the aerosol samples. These results confirm that Cyanobacteria are one of the candidate microorganisms responsible for lampenflora dispersion and are “alive and airborne” in caves.

Speleothem-Inspired Copper/Nickel Interfaces for Enhanced Liquid-Vapor Transport by Marangoni and Soret Effects.

Geological formations have superior wickability and support the absorption of water and oils into narrow spaces of Earth's crust without external assistance. In this study, we present speleothem inspired heterogeneous porous and wicked copper (Cu)/nickel (Ni) interfaces for enhanced nucleate boiling of water/ethanol mixtures for energy-efficient separation processes. The incorporation of Ni strands within the copper particle matrix significantly enhanced heat transfer. Compared to plain copper, the Cu/Ni speleothem surfaces exhibited a 61% increase in the heat transfer coefficient for water/ethanol mixtures and a 332% increase for water, with a 58% faster onset of nucleate boiling. This enhancement was attributed to Marangoni and Soret effects at the Cu/Ni interfaces, driven by surface tension and concentration gradients. Furthermore, the synergistic wicking action of the Ni strands facilitated rewetting of the surface, replenishing liquid to the porous nucleation sites and preventing surface dry-out, thereby improving the overall heat transfer performance.

Impact of water exhaled out by visitors in show caves: a case study from the Moravian Karst (Czech Republic)

The anthropogenic impact of the water and CO2 exhaled by visitors was studied in the show caves of the Moravian Karst (Czech Republic), especially in the Balcarka and Výpustek Caves. Two alternative models based on (1) the known/presumed composition of the breathed air and physical activity of visitors and (2) the detailed monitoring microclimatic data were proposed. The CO2 fluxes of 2.4 × 10−4 and (2.0–3.9) × 10−4 mol person−1 s−1 and the water vapor fluxes of (3.2–8.9) × 10−3 and (0.6–1.2) × 10−2 g person−1 s−1 were found for a slightly increased physical load. The total attendance and cave tour duration were the main driving factors. For the available data on attendance and accessibility periods, the total mass of water vapor exhaled by visitors in all show caves in the Moravian Karst was estimated between 9.6 × 106 and 4.3 × 108 g with significant seasonality. According to the geochemical model, this mass of water is capable of dissolving 1280 to 59,038 g of calcite, assuming a mean winter and summer CO2 concentration in the cave air of 1000 and 3000 ppmv. The larger extent of water condensation can lead to the so-called condensation corrosion, whereas the lower extent of condensation probably causes a recrystallization of calcite on the surface of speleothems and rocks.

Carbonate microbialites and chemotrophic microbes: Insights from caves from south‐east China

ABSTRACTChemosynthetic microorganisms facilitate microbialite development in many caves throughout the world. In Youqin Cave and Tian'e Cave, located in the Carboniferous–Triassic carbonates on the South China Block, five Quaternary speleothems (stalagmite, stalactite and cave pearl) that are 2.3 to 11.0 cm long were examined for their petrographic, geochemical and microbiological features to reveal how chemotrophs contribute to microbialite growth. In the speleothems, millimetre‐sized stromatolites, thrombolites and calcified microbial mats are characterized by alternating light, calcitic microlaminae and dark, clay and organic‐rich calcite microlaminae. Filamentous (reticulate, smooth, nodular and helical), coccoid and bacilliform microbes, originally carried into the caves from surface soils, are more common in the dark microlaminae/clots than in the light microlaminae. 16S rRNA gene sequencing shows that the biotas in the microbialites are dominated by chemoorganotrophic heterotrophic bacteria, including primarily Sphingomonas, Crossiella and Acinetobacter, and rare Archaea. Diverse metabolic pathways of these prokaryotes, including ureolysis, denitrification and nitrite ammonification, contributed to increases in localized pH and/or dissolved inorganic carbon in these microenvironments, prompting carbonate precipitation. Development of the cave microbialites was probably controlled by the evolution of the cave microbial community as environmental conditions changed. Microbialite growth was probably mediated by the microorganisms that flourished on the speleothem surfaces during periods of low drip water rates and slow calcite precipitation. The change from microstromatolites to microthrombolites was probably linked to a decrease in cell populations in the microbial communities. These cave microbialites provide clear insights regarding the biogenicity and growth mechanisms of chemosynthetic microbialites. Given their association with chemolithotrophic activities that can date back to the Meso‐Archean, cave microbialites provide insights into the biogenicity and growth mechanisms of chemosynthesis‐based microbialites throughout geological history.

Corrosion of carbonate speleothems by bat guano

Interactions between bat guano and speleothems were studied in caves of Slovakia (Domica, Drienovská, and Jasovská caves) and Poland (Nietoperzowa Cave). This contribution focuses on the estimation of the rate of guano-induced corrosion of carbonates and on the transformations of speleothems caused by the corrosion. The intense interaction between bat guano accumulations and cave carbonates is mainly controlled by the chemical composition of guano. Corrosion of carbonates by guano leachates, suggested by negative calcite saturation index, was confirmed by weight loss of experimental carbonate tablets exposed to interaction with guano in situ in caves, and under laboratory conditions. The calculated corrosion rate of the tablets was up to 0.111 mm/y. However, measurements of selected corrosion forms in the studied caves, compared to the guano 14C age, suggest rates of the corrosion up to 0.65 mm/y. Transport of aggressive guano leachates is possible in the presence of water; increased drip water supply is considered as contributing to the higher dissolution rates. Crystallization of phosphates as byproducts of the interaction of guano with carbonates can also alter the dissolution process. Phosphates, represented by ardealite, brushite, and hydroxylapatite, were observed on the surfaces of experimental tablets and speleothems alike. Interestingly, hydroxylapatite was the only mineral associated with guano-related hiatuses within speleothem sections. Phosphates are usually accompanied by various dissolution features, such as corrosion pits and considerably dissolved calcite crystals. Dissolution features currently forming on speleothem surfaces are analogous to those identified in the fossil record. U-series dating of guano corrosion episodes within stalagmites from Domica and Drienovská caves indicates their Pleistocene age, while within a flowstone from Nietoperzowa Cave, a Holocene age. Considerable guano accumulations are common in low-latitude caves, whereas in temperate climatic zones guano accumulates irregularly in space and time. The guano accumulations are usually restricted to cave sections distant no more than few hundred meters from the nearest entrance. Considering the widespread distribution of bats across the globe, this process is expected to be common in caves. Nevertheless, the random distribution of guano in caves and its temporal deposition, but also the climate-dependent availability of water, suggest that guano-induced corrosion can be regarded as a site specific process.

The distribution of fossil pollen and charcoal in stalagmites

AbstractPollen preserved in caves provides a little-appreciated opportunity to study past vegetation and climate changes in regions where conventional wetland sediments are either unavailable, contain little organic matter, and/or are difficult to date accurately. Most palynology in caves has focused on clastic infill sediments, but pollen preserved in growing speleothems provides important new opportunities to develop vegetation and climatic records that can be dated accurately with radiometric methods. However, when pollen is present in speleothems, concentrations can vary by orders of magnitude, highlighting how little we know about the processes that transport pollen into caves and onto speleothem surfaces, and that determine the pollen's preservation probability. To explore these aspects of speleothem pollen taphonomy, we investigated the distribution of pollen and microscopic charcoal within several stalagmites from southwest Australia. We examined spatial patterns in pollen and charcoal preservation in order to distinguish whether observed gradients result from preservation or are products of systematic transport processes working along stalagmite surfaces. We find that pollen grains and charcoal fragments are located preferentially on the flanks of most stalagmites. This suggests that pollen grain and charcoal deposition on speleothems is influenced by transport and accumulation of detrital debris on growing surfaces. These insights will assist in future sampling campaigns focusing on speleothem pollen and charcoal contents.

Healed speleothems: A possible indicator of seismotectonic activity in karst areas

Healed speleothems, sparsely mentioned in literature, have been noted in one of the side passages of the Demänová Cave System in Slovakia. Speleothem healing commonly proceeds in columns and flowstones after their brittle deformation. Crystallization of calcium carbonate in fractures and along their mouths results in formation of various outgrowths: subvertical ridges, subhorizontal ridges, and helictites. Morphology of the subvertical ridges and helictites indicates that they were supplied by water migrating through the fractures, while the subhorizontal ridges resulted from gravity-controlled water flow down the speleothem surface. Stable isotope composition of the outgrowths suggests that they crystallized as a result of CO2 degassing, like most speleothems. Since speleothem damages in the DCS are directly linked to fault reactivation, the healed speleothems appear to be advantageous objects for seismotectonic analysis of karst terrains.

The effects of drip rate and geometry on the isotopic composition of speleothems: Evaluation with an advection-diffusion-reaction model

The curvature and slope of speleothem surfaces have been shown to affect the reaction rates in the aqueous carbonate system by altering the thickness of the CaCO3-precipitating solution. However, the effects of speleothem geometry and drip rate on the speleothem’s carbon and oxygen isotopic composition have yet to be investigated. Over more strongly sloping surfaces, solutions are thinner and flow faster. The effects of thinner and faster-flowing solutions on the isotopic composition of carbonate minerals precipitated from these solutions are of opposite sense. Thinner solutions enhance rates of CO2 degassing and mineral formation, increasing the degree of isotopic distillation of the dissolved inorganic carbon (DIC) reservoir and leading to larger isotopic fractionation between the carbonate mineral and the initial DIC. Concurrently, faster flow over the steeper surfaces results in shorter residence times of the solutions on the growing speleothem, thereby limiting the degree of isotopic distillation and CaCO3-DIC fractionation. Consequently, predicting the CaCO3-DIC isotopic fractionation as a function of drip rate, surface slope and flow distance is not trivial.Using an advection-diffusion-reaction model, we tested the sensitivity of the isotopic composition of calcite precipitated along inclined surfaces to the solution discharge (drip) rate and the surface slope. Calcite δ13C and δ18O values correlate well with the degree of prior calcite precipitation (PCP), which is identified as a major determinant of isotopic compositions in speleothems. Our results show that at low PCP, speleothem δ13C and δ18O values may initially decrease relative to calcite-DIC and calcite-water equilibrium due to expression of kinetic isotope effects of mineral precipitation. Upon progressive PCP, δ13C and δ18O values gradually increase due to continuous CO2(aq) formation and degassing. This shift in the isotopic composition of the calcite to lower-than-equilibrium and then higher-than-equilibrium values expands the regime of near-equilibrium compositions during the isotopic evolution. In turn, this may allow quantitative environmental reconstructions, even when the isotopic system is in disequilibrium. Under the simulated conditions, our model predicts maximal potential enrichments of 7 and 3‰ in the calcite δ13C and δ18O values, respectively. In addition, we found a strong dependence of the calcite δ13C and δ18O values on the drip rate and distance of flow, and a weak dependence on the surface slope. In fact, changes in drip rate alone may drive isotopic offsets of several permil, when all other environmental parameters are kept constant. According to our model, higher drip rates and shorter stalactites promote closer-to-equilibrium isotopic compositions of stalagmites, providing a higher signal-to-noise ratio, and minimizing variability that is unrelated to climate.

Profiling of Bacteria Capable of Precipitating CaCO3 on the Speleothem Surfaces in Dupnisa Cave, Kırklareli, Turkey

This study aimed to identify the bacteria which take part in the CaCO3 precipitation on the speleothem surfaces of Dupnisa Cave. In addition, this study highlighted the CaCO3 precipitation ability of the bacteria with negative urease activity. 150 isolates with microbial induced calcium carbonate precipitation features were selected and identified. They were belonging to Proteobacteria (53.3%), Firmicutes (32.7%) and, Actinobacteria (4.7%) phyla. The dominant bacterial species on all surface samples were Bacillus mycoides (9.3%), Bacillus zhangzhouensis (5.3%), and Serratia quinivorans (4%). Our results showed that most of the bacteria which can precipitate calcium carbonate on the B4 medium at the first 3 days, have urease negative activity. Within this study, it has been emphasized that other mechanisms enabling the precipitation of CaCO3 besides the urease mechanism should also be investigated. EDS analyses confirmed that the crystals were predominantly composed of calcium, carbon, and oxygen. In addition, the EDS highlighted that the two strains of Bacillus mycoides, isolated from two different surfaces, produced crystals of different morphology. Our study results to the identification of the bacteria which contribute to the Dupnisa Cave walls formation. Besides, our results showed that the Dupnisa Cave is housing bacteria with biotechnological and engineering applications potentials.

Fungal communities in bat guano, speleothem surfaces, and cavern water in Madai cave, Northern Borneo (Malaysia)

ABSTRACT The island of Borneo is a global biodiversity hotspot. However, its limestone caves are one of its least-studied ecosystems. We report for the first time the fungal species richness, diversity and abundance from Madai cave, situated in north-eastern Borneo. Environmental samples from inside the cave environment were collected (guano, speleothem, and cavern water) via opportunistic sampling. The dilution method was performed for isolation of fungi. Morphological characterisation and molecular analysis of the ITS region were utilised for the identification of isolates. Fifty-five pure cultures of fungi were attained, comprising 32 species from 15 genera, eight orders, and two divisions, Ascomycota and Basidiomycota. Ascomycetes dominated the fungal composition, accounting for 53 (96%) out of 55 total isolates. Penicillium spp. accounted for more than 47.1% of fungal abundance in all sample types. However, Aspergillus spp. had the highest occurrence rate, being isolated from all environmental samples except one. Purpureocillium lilacinum was isolated most frequently, appearing in five separate samples across all three substrates. Annulohypoxylon nitens, Ganoderma australe, Pyrrhoderma noxium, and Xylaria feejeensis were discovered and reported for the first time from the cave environment. This study provides additional data for further research on the mycoflora of Sabah’s various ecosystems, especially limestone caves.

Glycerol dialkyl glycerol tetraethers (GDGT) distributions from soil to cave: Refining the speleothem paleothermometer

The glycerol dialkyl glycerol tetraether (GDGT) paleothermometer has potential application as a speleothem paleoclimate proxy. However, the sources of GDGTs found in speleothems are poorly understood, with multiple potential sources of GDGTs from the soil to the speleothem surface. Here we analysed GDGTs in soils, soil leachates, in-cave surfaces and cave drip waters at two Australian montane caves. We observed significantly different GDGT distributions between soils, soil leachates, in-cave surfaces and drip waters and significant spatial differences in in-cave GDGT distributions. Comparison with published modern in-cave and karst groundwater GDGT datasets from Australia, Europe and China shows that speleothem GDGT distributions are different from those of all potential sources. We hypothesise that speleothem surfaces have a calcifying, alkaline, oxic, wet, carbon-available, environment that supports a microbial community that is different from other possible karst GDGT sources. We propose that the presence of GDGTs related to anoxic or methanogenic conditions, and observed in cave drip water and on in-cave surfaces, can be used to identify GDGTs from these sources. We confirm that TEX86 based paleothermometers are robust speleothem GDGT paleothermometers, whose calibration can be further refined through improved understanding and measurement of cave temperatures.

Quantifying carbon isotope disequilibrium during in-cave evolution of drip water along discreet flow paths

Paleoclimate reconstructions that use speleothem proxy data have increased our understanding of terrestrial climate change, but gaps remain in our understanding of in-cave processes that influence speleothem chemistry. The δ13C values of speleothem calcite are typically influenced by kinetic isotope effects that operate during CO2 degassing and calcite precipitation. Therefore the identification and quantification of these isotopic effects is important in interpreting speleothem stable isotope records. Here we studied the change in water chemistry and δ13C values of dissolved inorganic carbon (DIC) along discreet flow paths at multiple drip sites in Inner Space Cavern, central Texas. We quantified the extent to which the water remains in C isotopic equilibrium during flow along speleothem surfaces as CO2 degasses and calcite precipitates.Two locations in the study cave that have long in-cave flow paths were examined to determine the geochemical evolution and its driving processes along these paths. At each location cave water was sampled at two points 1–2 meters apart along each flow path. Among the key spatial changes observed is a <∼1‰ to ∼4‰ increase in δ13C values of DIC along the flow paths. The magnitude of the increase in δ13C values is controlled by the extent of DIC loss to CO2 degassing. The extent of DIC loss and CO2 degassing is controlled by the pCO2 gradient between drip water and cave air. If the DIC loss is less than 15%, then the evolution of the δ13C value of the DIC reservoir can be accounted for by a Rayleigh distillation model with equilibrium C-isotope fractionation factors for (CO2(g)-HCO3−(aq)) and (CaCO3-HCO3−(aq)). As the depletion of the DIC reservoir exceeds 15% the DIC δ13C values become progressively higher such that the (HCO3−(aq)-CO2(g)) fractionation values needed to explain the observations change from equilibrium values of ∼8‰ to non-equilibrium values of up to ∼25‰. This variance in magnitude of C-isotope fractionation during CO2 degassing cannot be attributed to changes in temperature, and thus we infer significant kinetic isotope effects at higher rates of DIC loss. Such kinetic effects have significant implications for speleothem C-isotope proxy interpretations, as these kinetic isotope effects are of a similar magnitude as those used to infer past changes in drought and vegetation.

Microbial Diversity and Mineralogical-Mechanical Properties of Calcitic Cave Speleothems in Natural and in Vitro Biomineralization Conditions.

Natural mineral formations are a window into important processes leading to carbon storage and mineralized carbonate structures formed through abiotic and biotic processes. In the current study, we made an attempt to undertake a comprehensive approach to characterize the mineralogical, mechanical, and microbial properties of different kinds of speleothems from karstic caves; with an aim to understand the bio-geo-chemical processes in speleothem structures and their impact on nanomechanical properties. We also investigated the biomineralization abilities of speleothem surface associated microbial communities in vitro. Mineralogical profiling using techniques such as X-ray powder Diffraction (XRD) and Tescan Integrated Mineral Analyzer (TIMA) demonstrated that calcite was the dominant mineral in the majority of speleothems with Energy Dispersive X-ray Analysis (EDS) indicating a few variations in the elemental components. Differing proportions of polymorphs of calcium carbonate such as aragonite and vaterite were also recorded. Significant variations in trace metal content were recorded through Inductively Coupled Plasma Mass Spectrometer (ICP-MS). Scanning Electron Microscopy (SEM) analysis revealed differences in morphological features of the crystals which varied from triangular prismatic shapes to etched spiky forms. Microbial imprints and associations were seen in a few sections. Analysis of the associated microbial diversity showed significant differences between various speleothems at Phylum level; although Proteobacteria and Actinobacteria were found to be the predominant groups. Genus level microbial associations showed a relationship with the geochemistry, mineralogical composition, and metal content of the speleothems. The assessment of nanomechanical properties measured by Nanoindentation revealed that the speleothems with a dominance of calcite were stronger than the speleothems with mixed calcium carbonate polymorphs and silica content. The in vitro metabolic activity of the microbial communities associated with the surfaces of the speleothems resulted in calcium carbonate crystal precipitation. Firmicutes and Proteobacteria dominated these populations, in contrast to the populations seen in natural systems. The precipitation of calcium carbonate crystals in vitro indicated that microbial metabolic activity may also play an important role in the synthesis and dissociation of biominerals in the natural environment. Our study provides novel evidence of the close relationship between mineralogy, microbial ecology, geochemistry, and nanomechanical properties of natural formations.

The effect of speleothem surface slope on the remanent magnetic inclination

AbstractSpeleothems are of interest for high‐resolution reconstruction of the Earth's magnetic field. However, little is known about the influence of speleothem morphologies on their natural remanent magnetization (NRM) record. Here we report on a high‐resolution paleomagnetic study of a dome‐shaped speleothem of middle Holocene age from southern Portugal, with special attention to the anisotropy of magnetic susceptibility (AMS) and anisotropy of anhysteretic remanent magnetization (AARM). To assess the potential influence of the slope of the speleothem surface on the recorded remanent magnetization, we compare magnetic directions and AMS and AARM fabrics from subhorizontal to gradually subvertical calcite growth layers collected in a transversal cross section of the speleothem. A linear correlation is observed between magnetic inclinations, calcite laminae slope, and AARM k1 inclination. The AMS fabric is mostly controlled by calcite crystals, with direction of the minimum axes (k3) perpendicular to laminae growth. Magnetic inclinations recorded in inclined and vertical calcite growth layers are underestimated when compared to a global paleosecular variation (PSV) model. After extrapolating magnetic inclinations to the horizontal, the corrected data better fit the PSV model but are still lower than the predicted magnetic inclinations, suggesting that inclination shallowing affects the entire speleothem. We suggest that speleothem morphology exerts a critical role on the magnetic inclination recording, which is controlled by the Earth's magnetic field but also influenced by particle rolling along the sloping surfaces. These observations open new avenues for reconstructing high‐resolution paleomagnetic secular variation records from speleothems and provide new insights into their NRM acquisition mechanisms.

Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO32− concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at ≈1.1mol/mol. Within the analyzed ranges of pH (8.2–8.6), CO32− concentration (1–6mg/L), supersaturation (SIaragonite: 0.08–1.08; SIcalcite: 0.23–1.24), drip rate (0.2–81drops/min) and dissolved Zn (6–90μg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above ∼1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at ∼11°C from dripwaters with initial Mg/Ca approaching ∼1.1 incorporate ∼5mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is favored from a solubility viewpoint. We also show that unaccounted CaCO3 precipitation in intermediate sampling containers and splash effects may in cases result in underestimating dripwater Ca concentration and alkalinity, potentially leading to incorrect conclusions regarding the role of fluid Mg/Ca ratio and supersaturation on CaCO3 mineralogy. A simple way to elude the first effect is by taking water samples directly from stalactites and by titrating alkalinity in the same containers used to collect dripwaters.

Application of Scanning Electron Microscopy/Energy-Dispersive X-Ray Spectroscopy for Characterization of Detrital Minerals in Karst Cave Speleothems.

Micro-scale observations in karst caves help to identify different processes that shaped local morphology. Scanning electron microscopy/energy-dispersive X-ray spectroscopy inspection of speleothems from two karst caves in Slovenia, Predjama and Črna Jama, confirmed the presence of sub-angular to sub-rounded detrital fragments of clay minerals, feldspars, quartz, Fe-oxides/hydroxides, rutile and Nb-rutile, xenotime, kassite, allanite, fluorapatite, epidote, ilmenite, monazite, sphene, and zircon, between 2 and 50 μm across. These occur in porous layers separating calcite laminae in the clayey coating on the layer below the surface of the speleothems, and are also incorporated within actual crystals. It is likely that they are derived from the weathered rocks of the Eocene flysch. Probably they were first transported into the caves by floodwaters forming cave sediments. Later, depending upon the climate conditions, they were moved by air currents or by water to the surface of active speleothems. They might also be redeposited from overlying soils enriched with wind-transported minerals from the flysch, or from higher passages filled with weathered flysch sediment, by drip water percolating through the fissured limestone. As some of the identified minerals are carriers of rare earth elements, Ti and Zr, their presence could affect any palaeoclimatic interpretations that are based upon the geochemical composition of the speleothems.

Stable isotope data as constraints on models for the origin of coralloid and massive speleothems: The interplay of substrate, water supply, degassing, and evaporation

Many speleothems can be assigned to one of two morphological groups: massive speleothems, which consist of compact bulks of material, and coralloids, which are domal to digitate in form. Faster growth on protrusions of the substrate occurs in the typical growth layers of coralloids (where those layers are termed “coralloid accretions”), but it is not observed in the typical layers of massive speleothems, which in contrast tend to smoothen the speleothem surface (and can therefore be defined as “smoothing accretions”). The different growth rates on different areas of the substrate are explainable by various mechanisms of CaCO3 deposition (e.g., differential aerosol deposition, differential CO2 and/or H2O loss from a capillary film of solution, deposition in subaqueous environments). To identify the causes of formation of coralloids rather than massive speleothems, this article provides data about δ13C and δ18O at coeval points of both smoothing and coralloid accretions, examining the relationship between isotopic composition and the substrate morphology. In subaerial speleothems, data show enrichment in heavy isotopes both along the direction of water flow and toward the protrusions. The first effect is due to H2O evaporation and CO2 degassing during a gravity-driven flow of water (gravity stage) and is observed in smoothing accretions; the second effect is due to evaporation and degassing during water movement by capillary action from recesses to prominences (capillary stage) and is observed in subaerial coralloids. Both effects coexist in smoothing accretions interspersed among coralloid ones (intermediate stage). Thus this study supports the origin of subaerial coralloids from dominantly capillary water and disproves their origin by deposition of aerosol from the cave air. On the other hand, subaqueous coralloids seem to form by a differential mass-transfer from a still bulk of water toward different zones of the substrate along diffusion flux vectors of nutrients perpendicular to the iso-depleted surfaces. Finally, this isotopic method has proved useful to investigate the controls on speleothem morphology and to obtain additional insights on the evolution of aqueous solutions inside caves.

Making a living while starving in the dark: metagenomic insights into the energy dynamics of a carbonate cave

Carbonate caves represent subterranean ecosystems that are largely devoid of phototrophic primary production. In semiarid and arid regions, allochthonous organic carbon inputs entering caves with vadose-zone drip water are minimal, creating highly oligotrophic conditions; however, past research indicates that carbonate speleothem surfaces in these caves support diverse, predominantly heterotrophic prokaryotic communities. The current study applied a metagenomic approach to elucidate the community structure and potential energy dynamics of microbial communities, colonizing speleothem surfaces in Kartchner Caverns, a carbonate cave in semiarid, southeastern Arizona, USA. Manual inspection of a speleothem metagenome revealed a community genetically adapted to low-nutrient conditions with indications that a nitrogen-based primary production strategy is probable, including contributions from both Archaea and Bacteria. Genes for all six known CO2-fixation pathways were detected in the metagenome and RuBisCo genes representative of the Calvin-Benson-Bassham cycle were over-represented in Kartchner speleothem metagenomes relative to bulk soil, rhizosphere soil and deep-ocean communities. Intriguingly, quantitative PCR found Archaea to be significantly more abundant in the cave communities than in soils above the cave. MEtaGenome ANalyzer (MEGAN) analysis of speleothem metagenome sequence reads found Thaumarchaeota to be the third most abundant phylum in the community, and identified taxonomic associations to this phylum for indicator genes representative of multiple CO2-fixation pathways. The results revealed that this oligotrophic subterranean environment supports a unique chemoautotrophic microbial community with potentially novel nutrient cycling strategies. These strategies may provide key insights into other ecosystems dominated by oligotrophy, including aphotic subsurface soils or aquifers and photic systems such as arid deserts.

Profiling Bacterial Diversity and Taxonomic Composition on Speleothem Surfaces in Kartchner Caverns, AZ

Caves are relatively accessible subterranean habitats ideal for the study of subsurface microbial dynamics and metabolisms under oligotrophic, non-photosynthetic conditions. A 454-pyrotag analysis of the V6 region of the 16S rRNA gene was used to systematically evaluate the bacterial diversity of ten cave surfaces within Kartchner Caverns, a limestone cave. Results showed an average of 1,994 operational taxonomic units (97 % cutoff) per speleothem and a broad taxonomic diversity that included 21 phyla and 12 candidate phyla. Comparative analysis of speleothems within a single room of the cave revealed three distinct bacterial taxonomic profiles dominated by either Actinobacteria, Proteobacteria, or Acidobacteria. A gradient in observed species richness along the sampling transect revealed that the communities with lower diversity corresponded to those dominated by Actinobacteria while the more diverse communities were those dominated by Proteobacteria. A 16S rRNA gene clone library from one of the Actinobacteria-dominated speleothems identified clones with 99 % identity to chemoautotrophs and previously characterized oligotrophs, providing insights into potential energy dynamics supporting these communities. The robust analysis conducted for this study demonstrated a rich bacterial diversity on speleothem surfaces. Further, it was shown that seemingly comparable speleothems supported divergent phylogenetic profiles suggesting that these communities are very sensitive to subtle variations in nutritional inputs and environmental factors typifying speleothem surfaces in Kartchner Caverns.