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Speleology in Kazakhstan

Shakalov on 04 Jul, 2018
Hello everyone!   I pleased to invite you to the official site of Central Asian Karstic-Speleological commission ("Kaspeko")   There, we regularly publish reports about our expeditions, articles and reports on speleotopics, lecture course for instructors, photos etc. ...

New publications on hypogene speleogenesis

Klimchouk on 26 Mar, 2012
Dear Colleagues, This is to draw your attention to several recent publications added to KarstBase, relevant to hypogenic karst/speleogenesis: Corrosion of limestone tablets in sulfidic ground-water: measurements and speleogenetic implications Galdenzi,

The deepest terrestrial animal

Klimchouk on 23 Feb, 2012
A recent publication of Spanish researchers describes the biology of Krubera Cave, including the deepest terrestrial animal ever found: Jordana, Rafael; Baquero, Enrique; Reboleira, Sofía and Sendra, Alberto. ...

Caves - landscapes without light

akop on 05 Feb, 2012
Exhibition dedicated to caves is taking place in the Vienna Natural History Museum   The exhibition at the Natural History Museum presents the surprising variety of caves and cave formations such as stalactites and various crystals. ...

Did you know?

That aquifer is 1. a formation, group of formations, or part of a formation that contains sufficient saturated permeable material to yield significant quantities of water to wells and springs [6]. 2. a ground-water reservoir. 3. pervious rock that is completely saturated and will yield water to a well or spring. historically the term has been applied to beds favoring early cave development, probably synonymous with some inception horizons [18].?

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KarstBase a bibliography database in karst and cave science.

Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
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Featured articles from other Geoscience Journals
Karst environment, Culver D.C.
Mushroom Speleothems: Stromatolites That Formed in the Absence of Phototrophs, Bontognali, Tomaso R.R.; D’Angeli Ilenia M.; Tisato, Nicola; Vasconcelos, Crisogono; Bernasconi, Stefano M.; Gonzales, Esteban R. G.; De Waele, Jo
Calculating flux to predict future cave radon concentrations, Rowberry, Matt; Marti, Xavi; Frontera, Carlos; Van De Wiel, Marco; Briestensky, Milos
Microbial mediation of complex subterranean mineral structures, Tirato, Nicola; Torriano, Stefano F.F;, Monteux, Sylvain; Sauro, Francesco; De Waele, Jo; Lavagna, Maria Luisa; D’Angeli, Ilenia Maria; Chailloux, Daniel; Renda, Michel; Eglinton, Timothy I.; Bontognali, Tomaso Renzo Rezio
Evidence of a plate-wide tectonic pressure pulse provided by extensometric monitoring in the Balkan Mountains (Bulgaria), Briestensky, Milos; Rowberry, Matt; Stemberk, Josef; Stefanov, Petar; Vozar, Jozef; Sebela, Stanka; Petro, Lubomir; Bella, Pavel; Gaal, Ludovit; Ormukov, Cholponbek;
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Your search for disequilibrium (Keyword) returned 19 results for the whole karstbase:
Showing 1 to 15 of 19
Measurements of uranium series disequilibrium in the case-hardened Aymamon limestone in Puerto Rico., 1984, Ivanovich M. , Ireland P.

Uranium-series Disequilibrium: Applications to Earth, Marine Environmental Sciences, 1992, Ivanovich M. , Harmon R. S.

Palaeosecular variation observed in speleothems from western China and northern Spain, PhD thesis, 1996, Openshaw, S. J.

This study has produced records of the palaeosecular variation (PSV) of the earth's magnetic field from Speleothems from China and Spain. The ultimate aim of this project was to produce contemporaneous PSV records which would show that Speleothems accurately record ambient geomagnetic field behaviour. From Sichuan Province, China, five Speleothems were collected of which four were studied for their records of PSV. Eight Spanish Speleothems from the Cantabrian coast were collected but their weak magnetisation allowed only one record of PSV to be produced.
All speleothem sub-samples were weakly magnetised and had, on average, initial intensities of <100 x 10-8 Am2kg-1. Despite this, the majority of sub-samples were stable during stepwise alternating-field and thermal demagnetisation and each displayed a single component of magnetisation after removal of any secondary overprints. Rock magnetic experiments were hampered by low mineral concentrations but suggested that the remanences of each speleothem were carried by a mixture of multi and single-domain (titano-) magnetite and also by haematite present in significant quantities. The primary method of remanence acquisition appeared to be a depositional remanence sourced from flooding. This was corroborated by a linear relationship between sub-sample intensities and weight % acid insoluble detritus.
A selection of sub-samples from each speleothem were dated using uranium-thorium disequilibrium and alpha spectrometry. For the majority of sub-samples the low concentrations of uranium, high levels of detrital contamination and initially low chemical yields raised the associated dating inaccuracies above the quoted level for alpha spectrometry of 5-10%. Two Spanish Speleothems had high uranium concentrations and little, or no, detrital contamination. Percent age errors of these Speleothems ranged from 1 to 6%. Comprehensive experiments on the efficiencies of three electrodeposition methods were also undertaken. The most efficient method was found to be a modified version of the Hallstadius method (Hallstadius, 1984), which consistently achieved chemical yields between 40 and 90% for uranium and thorium.
In order to correct more analytically for the presence of detrital contamination, the leachate/leachate method of Schwarcz and Latham (1989) was tested. The maximum likelihood estimation data treatment technique (Ludwig and Titterington, 1994) was used to calculate dates from these analyses. Tests on Mexican speleothem SSJ2 gave excellent results allowing a revised dating scheme to be adopted. Tests on some sub-samples from Chinese Speleothems were generally unsuccessful due to analytical errors.
The isotope 210Pb was used to date the top surface of one speleothem. A constant growth rate was inferred which was significantly less than that calculated from the 230Th - 234U dating method. This was thought to be due to the former techniques inability to resolve growth rates of periods of less than 200 years.
Despite the dating errors associated with each speleothem the records of PSV compare well with each other and with contemporaneous records from China, Japan and also the UK (for the Spanish record). In addition. agreement with PSV data modelled from observatory records suggested that westward drift of the non-dipole geomagnetic field was predominant during the past 10ka.

Dedolomitization as a driving mechanism for karst generation in Permian Blaine formation, southwestern Oklahoma, USA, 1997, Raines M. A. , Dewers T. A. ,
Cyclic deposits of Permian shales, dolomites, and halite and gypsum-bearing strata in the Blaine Formation of Southwestern Oklahoma contain abundant karst features. The present study shows that an important mechanism of karst development in these sequences is dedolomitization, wherein gypsum and dolomite in close spatial proximity dissolve and supersaturate groundwaters with respect to calcite. The net loss of mass accompanying this process (dolomite and gypsum dissolution minus calcite precipitation) can be manifest in secondary porosity development while the coupled nature of this set of reactions results in the retention of undersaturated conditions of groundwater with respect to gypsum. The continued disequilibrium generates karst voids in gypsum-bearing aquifers, a mineral-water system that would otherwise rapidly equilibrate. Geochemical modeling (using the code PHRQPITZ, Plummer et al 1988) of groundwater chemical data from Southwestern Oklahoma from the 1950's up to the present suggests that dedolomitization has occurred throughout this time period in evaporite sequences in Southwestern Oklahoma. Reports from groundwater well logs in the region of vein calcite suggest secondary precipitation, an observation in accord with dedolomite formation In terms of the amounts of void space produced by dissolution, dedolomitization can dominate gypsum dissolution alone, especially in periods of quiescent aquifer recharge when gypsum-water systems would have otherwise equilibrated and karst development ceased. Mass balance modeling plus molar volume considerations show that for every cubic cm of original rock (dolomite plus gypsum), there is 0.54 cm(3) of calcite and 0.47 cm(3) of void space produced Only slightly more pore space results if the dedolomitization reaction proceeds by psuedomorphic replacement of dolomite by calcite than in a reaction mechanism based on conservation of bicarbonate

Dynamique sedimentaire et paleoenvironnements durant la transition Weichselien-Holocene a partir des depots endokarstiques de la Grotte de Han-sur-Lesse (Belgique), 1999, Blockmans S, Quinif Y, Bini A, Zuccoli L,
The cave sediments in the galleries near the entrance of the Han-sur-Lesse cave constitute a sedimentary record of the palaeoenvironmental evolution during the end of the Pleistocene, tardi-glacial transition and the Holocene. Lithostratigraphic study and granulometric analysis of three sections (the section of the 'Galeries des Potirons', the section of the 'Cave a Vin', the section of the 'Galerie des Petites Fontaines') enable to reconstruct the hydrological evolution of those galleries at the end of the last glacial period. This reconstruction is dated by uranium-series disequilibrium datings on speleothems and 14 C datings on charcoals

Calcite Fabrics, Growth Mechanisms, and Environments of Formation in Speleothems from the Italian Alps and Southwestern Ireland, 2000, Frisia S, Borsato A, Fairchild Ij, Mcdermott F,
Five fabrics were identified in Alpine and Irish caves on the basis of morphological and microstructural characteristics, and related to growth mechanisms and growth environment. Columnar and fibrous fabrics grow when speleothems are continuously wet, and from fluids at near-equilibrium conditions (low supersaturation; SIcc < 0.35), through the screw dislocation mechanism. The highly defective microcrystalline fabrics form at the same supersaturation range as columnar fabric but under variable discharge and the presence of growth inhibitors. Dendritic fabrics, which have the highest density of crystal defects, develop in disequilibrium conditions (high supersaturation) under periodic very low-flow-regime periods that result in prolonged outgassing. Cave calcareous tufa forms in disequilibrium conditions. Only the calcite crystals of fabrics formed at low supersaturation seem to precipitate near-isotopic-equilibrium conditions

Depositional and post-depositional history of warm stage deposits at Knocknacran, Co. Monaghan, Ireland: implications for preservation of Irish last interglacial deposits, 2004, Vaughan A. P. M. , Dowling L. A. , Mitchell F. J. G. , Lauritzen S. E. , Mccabe A. M. , Coxon P. ,
Organic-rich deposits, uncovered during overburden removal from mantled gypsum karst at Knocknacran opencast gypsum mine, Co. Monaghan, are the best candidate to date for a last interglacial record in Ireland. The two till and organic-rich deposits (preserved at different quarry elevations) were emplaced on to a Tertiary dolerite surface during high-energy flood events and subsequently folded and faulted by movement towards sinkholes in underlying gypsum. Uranium-thorium disequilibrium dating suggests that the organic-rich deposits in the upper section were hydrologically isolated at ca. 41 ka and those in the lower section at ca. 86 ka. Interpretation of the pollen content, although tentative because of the depositional and post-depositional history of the material, suggests that the organic material originated in a warm stage possibly warmer than the post-Eemian interstadials. The unusual setting of preservation may indicate that in situ, last interglacial deposits have generally been removed by erosion in Ireland.

Calcite dissolution kinetics and solubility in Na-Ca-Mg-Cl brines of geologically relevant composition at 0.1 to 1 bar pCO2 and 25 to 80°C. Doctoral dissertation, Texas A&M University. , 2005, Gledhill, Dwight Kuehl

Sedimentary basins can contain close to 20% by volume pore fluids that are commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of processes such as migration, dispersive mixing, or anthropogenic injection of CO2. This study measured calcite solubility and dissolution rates in geologically relevant Na-Ca-Mg-Cl synthetic brines (35 to 200 g L-1 TDS). In brines < 50 g L-1 TDS, the EQPITZER calculated calcium carbonate ion activity product (IAP) at steady-state was in reasonable agreement (±10%) with the thermodynamic solubility constant for calcite (Kc). However, the IAP systematically exceeded Kc in more concentrated brines. The deviation was strongly correlated with calcium concentration and also was observed in magnesium-free solutions. This is interpreted as an uncertainty in the carbonate ion activity coefficient, and minor adjustment in stoichiometric association constants (K*M2+CO30) for the CaCO30 or MgCo30 ion pairs would correct for the error. The dissolution rate dependency on brine composition, pCO2 (0.1 to 1 bar), and temperature (25.0 to 82.5 °C) was modeled using the empirical rate equation ()nkRΩ−=1 where R is the rate, k and n are empirical fitting terms, and Ω the degree of disequilibrium with respect to calcite. When Ω was defined relative to an apparent kinetic solubility, n could be assumed first-order over the range of Ω investigated (Ω = 0.2 to 1.0). Rates increased with increasing pCO2 as did the sensitivity to brine concentration. At 0.1 bar, rates were nearly independent of concentration (k = 13.0 ±2.0 x 10-3 moles m-1 hr-1). However, at higher CO2 partial pressures rates became composition dependent and the rate constant, k, was shown to be a function of temperature, pCO2, ionic strength, and calcium and magnesium activity. The rate constant (k) can be estimated from a multiple regression (MR) model of the form k = B0 + B1(T) + B2(pCo2) + B4(aCa2+) + B5(aMg2+). A relatively high activation energy (Ea = 20 kJ mol-1) was measured, along with a stirring rate independence suggesting the dissolution is dominated by surface controlled processes at saturation states Ω > 0.2 in these calcium-rich brines. These findings offer important implications to reaction-transport models in carbonate-bearing saline reservoirs.

U-Pb Isotopic Age of the StW 573 Hominid from Sterkfontein, South Africa, 2006, Walker Joanne, Cliff Robert A. , Latham Alfred G. ,
Sterkfontein cave, South Africa, has yielded an australopith skeleton, StW 573, whose completeness has excited great interest in paleoanthropology. StW 573, or 'Little Foot,' was found 25 meters below the surface in the Silberberg Grotto. 238U-206Pb measurements on speleothems immediately above and below the fossil remains, corrected for initial 234U disequilibrium, yield ages of 2.17 {} 0.17 million years ago (Ma) and [IMG]f1.gif' ALT='Formula' BORDER='0'> Ma, respectively, indicating an age for StW 573 of close to 2.2 Ma. This age is in contrast to an age of [~]3.3 Ma suggested by magnetochronology and ages of [~]4 Ma based on 10Be and 26Al, but it is compatible with a faunal age range of 4 to 2 Ma

UPb geochronology of speleothems by MC-ICPMS, 2006, Woodheada Jon, Hellstroma John, Maasa Roland, Drysdaleb Russell, Zanchettac Giovanni, Devined Paul, Taylor Eve

Building upon the work of Richards et al. [1998. U–Pb dating of a speleothem of Quaternary age. Geochimica et Cosmochimica Acta 62, 3683–3688], we have developed a method for precise dating of speleothems beyond the range of the U–Th technique using the U–Pb decay scheme. By coupling low-blank sample preparation procedures and multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) analytical methodologies developed for low-level Pb-isotope analysis, we find that, under ideal circumstances (radiogenic speleothems with very low common Pb), U–Pb dating of speleothems is not only possible, but also produces excellent age resolution— often comparable to or better than U–Th studies. Corrections for initial isotopic disequilibrium are necessary and exert a strong control on the achievable age uncertainty. The technique will be of immediate benefit in extending speleothem-based climate proxy records beyond _500 ka and will also find other uses, such as the dating of associated sub-fossil remains, and providing constraints on rates of landscape evolution and neo-tectonic processes. Here we present initial results for speleothems from the Nullarbor Plain, Western Australia, and the Alpi Apuane, Italy. The Nullarbor samples provide important new constraints on the development of aridity in Australia during the late Tertiary/early Quaternary, while the Apuane samples offer insights into the landscape history and uplift of that region.

A Pleistocene chronology for the fauna and artefacts of Cow Cave, Devon, UK, 2007, Lundberg, Joyce, Jim Simons And Donald Mcfarlane.
Cow Cave is a well-known archaeological and palaeontological site in the wall of Chudleigh Gorge, Devon, England. The cave is choked after a short distance with allochthonous sediments and speleothem accumulations. Palaeontological excavations at the cave in 1927 to 1935, and again in 1962 to 1963, yielded a rich Pleistocene fauna and several stone tools. However, in the absence of radiometric dating, the faunal composition was ambiguous with respect to age. Here, we report the first radiometric dates on the site. Two Thermal Ionization Mass spectrometric uranium series disequilibrium dates place a critical speleothem layer from within the Cow Cave sediments in the warmer intervals of the MIS 6 glacial period, and suggest that the basal sediments entrained a fauna and human artefacts from the preceding MIS 7 interglacial period, the Aveley.

Hypogene Speleogenesis: Hydrogeological and Morphogenetic Perspective., 2007, Klimchouk A. B.

This book provides an overview of the principal environments, main processes and manifestations of hypogenic speleogenesis, and refines the relevant conceptual framework. It consolidates the notion of hypogenic karst as one of the two major types of karst systems (the other being epigenetic karst). Karst is viewed in the context of regional groundwater flow systems, which provide the systematic transport and distribution mechanisms needed to produce and maintain the disequilibrium conditions necessary for speleogenesis. Hypogenic and epigenic karst systems are regularly associated with different types, patterns and segments of flow systems, characterized by distinct hydrokinetic, chemical and thermal conditions. Epigenic karst systems are predominantly local systems, and/or parts of recharge segments of intermediate and regional systems. Hypogenic karst is associated with discharge regimes of regional or intermediate flow systems.

Various styles of hypogenic caves that were previously considered unrelated, specific either to certain lithologies or chemical mechanisms are shown to share common hydrogeologic genetic backgrounds. In contrast to the currently predominant view of hypogenic speleogenesis as a specific geochemical phenomenon, the broad hydrogeological approach is adopted in this book. Hypogenic speleogenesis is defined with reference to the source of fluid recharge to the cave-forming zone, and type of flow system. It is shown that confined settings are the principal hydrogeologic environment for hypogenic speleogenesis. However, there is a general evolutionary trend for hypogenic karst systems to lose their confinement due to uplift and denudation and due to their own expansion. Confined hypogenic caves may experience substantial modification or be partially or largely overprinted under subsequent unconfined (vadose) stages, either by epigenic processes or continuing unconfined hypogenic processes, especially when H2S dissolution mechanisms are involved.

Hypogenic confined systems evolve to facilitate cross-formational hydraulic communication between common aquifers, or between laterally transmissive beds in heterogeneous soluble formations, across cave-forming zones. The latter originally represented low-permeability, separating units supporting vertical rather than lateral flow. Layered heterogeneity in permeability and breaches in connectivity between different fracture porosity structures across soluble formations are important controls over the spatial organization of evolving ascending hypogenic cave systems. Transverse hydraulic communication across lithological and porosity system boundaries, which commonly coincide with major contrasts in water chemistry, gas composition and temperature, is potent enough to drive various disequilibrium and reaction dissolution mechanisms. Hypogenic speleogenesis may operate in both carbonates and evaporites, but also in some clastic rocks with soluble cement. Its main characteristic is the lack of genetic relationship with groundwater recharge from the overlying or immediately adjacent surface. It may not be manifest at the surface at all, receiving some expression only during later stages of uplift and denudation. In many instances, hypogenic speleogenesis is largely climate- independent.

There is a specific hydrogeologic mechanism inherent in hypogenic transverse speleogenesis (restricted input/output) that suppresses the positive flow-dissolution feedback and speleogenetic competition in an initial flowpath network. This accounts for the development of more pervasive channeling and maze patterns in confined settings where appropriate structural prerequisites exist. As forced-flow regimes in confined settings are commonly sluggish, buoyancy dissolution driven by either solute or thermal density differences is important in hypogenic speleogenesis.

In identifying hypogenic caves, the primary criteria are morphological (patterns and meso-morphology) and hydrogeological (hydrostratigraphic position and recharge/flow pattern viewed from the perspective of the evolution of a regional groundwater flow system). Elementary patterns typical for hypogenic caves are network mazes, spongework mazes, irregular chambers and isolated passages or crude passage clusters. They often combine to form composite patterns and complex 3- D structures. Hypogenic caves are identified in various geological and tectonic settings, and in various lithologies. Despite these variations, resultant caves demonstrate a remarkable similarity in cave patterns and meso-morphology, which strongly suggests that the hydrogeologic settings were broadly identical in their formation. Presence of the characteristic morphologic suites of rising flow with buoyancy components is one of the most decisive criteria for identifying hypogenic speleogenesis, which is much more widespread than was previously presumed. Hypogenic caves include many of the largest, by integrated length and by volume, documented caves in the world.

The refined conceptual framework of hypogenic speleogenesis has broad implications in applied fields and promises to create a greater demand for karst and cave expertise by practicing hydrogeology, geological engineering, economic geology, and mineral resource industries. Any generalization of the hydrogeology of karst aquifers, as well as approaches to practical issues and resource prospecting in karst regions, should take into account the different nature and characteristics of hypogenic and epigenic karst systems. Hydraulic properties of karst aquifers, evolved in response to hypogenic speleogenesis, are characteristically different from epigenic karst aquifers. In hypogenic systems, cave porosity is roughly an order of magnitude greater, and areal coverage of caves is five times greater than in epigenic karst systems. Hypogenic speleogenesis commonly results in more isotropic conduit permeability pervasively distributed within highly karstified areas measuring up to several square kilometers. Although being vertically and laterally integrated throughout conduit clusters, hypogenic systems, however, do not transmit flow laterally for considerable distances. Hypogenic speleogenesis can affect regional subsurface fluid flow by greatly enhancing initially available cross- formational permeability structures, providing higher local vertical hydraulic connections between lateral stratiform pathways for groundwater flow, and creating discharge segments of flow systems, the areas of low- fluid potential recognizable at the regional scale. Discharge of artesian karst springs, which are modern outlets of hypogenic karst systems, is often very large and steady, being moderated by the high karstic storage developed in the karstified zones and by the hydraulic capacity of an entire artesian system. Hypogenic speleogenesis plays an important role in conditioning related processes such as hydrothermal mineralization, diagenesis, and hydrocarbon transport and entrapment.

An appreciation of the wide occurrence of hypogenic karst systems, marked specifics in their origin, development and characteristics, and their scientific and practical importance, calls for revisiting and expanding the current predominantly epigenic paradigm of karst and cave science.


The Cueva de las Velas is the last cave unveiled at -290 level within the Naica Mine; the cavity has been intercepted by a mine gallery at the beginning of 2005. One of its peculiarities is the widespread thick deposits of diagenetic minerals deposited over the cave walls before the beginning of the evolution of the giant gypsum crystals. These deposits consist of complex, often scarcely crystalline iron-manganese-lead oxides-hydroxides, but carbonates, sulphates and silicates are also present. Other minerals, mainly sulphates, started developing just after this area of the mine was dewatered some 20 years ago. Presently 17 different minerals have been observed, 5 of which (orientite, starkeyite, szmolnokite, szmikite and woodruffite) are completely new for the cavern environment. The study of these minerals, together with the presence of a completely new type of gypsum crystals, allowed to improve the knowledge on the speleogenetic evolution of this cave, which seems to be by far more complex than that of the other cavity of the -290 level. Its complexity is reflected by the activity of a larger number of different speleogenetic mechanisms. Among them are worth of mention the thermal corrosion/dissolution, the anhydrite- gypsum disequilibrium, the acid aggression, and the capillary migration and evaporation.

230Th/U-dating of fossil corals and speleothems, 2008, Scholz D. , Hoffmann D.

Both marine and terrestrial carbonates can be precisely dated by U-series disequilibrium methods in the age range <600 ka (thousands of years). Here we focus on 230Th/U-dating of reef corals and speleothems. The requirements, potential but also the problems of 230Th/U-dating of both archives are presented and discussed. Fossil reef corals are used as indicators for past sea level fluctuations and as high-resolution palaeoclimate archives. These applications require precise and accurate dating, which can be achieved using 230Th/U-dating. However, many fossil corals show evidence for post-depositional open-system behaviour. This limits the accuracy of 230Th/U-ages of fossil corals rather than the analytical precision. We present and discuss the currently available methods to identify altered corals and also review three recently developed open-system dating approaches. Speleothems are very important climate archives because they are found in most continental areas and can be used to investigate and directly compare spatially variable climate conditions. They usually show no evidence for open-system behaviour but may contain significant amounts of initial detrital 230Th. We discuss the currently available correction techniques and methods to derive the most reliable ages. Furthermore, we give an overview of the state of the art techniques for U-series isotopes measurements. 

Formation of seasonal ice bodies and associated cryogenic carbonates in Caverne de lOurs, Que bec, Canada: Kinetic isotope effects and pseudo-biogenic crystal structures, 2009, Lacelle D. , Lauriol B. , And Clark I. D.
This study examines the kinetics of formation of seasonal cave ice formations (stalagmites, stalactites, hoar, curtain, and floor ice) and the associated cryogenic calcite powders in Caverne de lOurs (QC, Canada), a shallow, thermally-responsive cave. The seasonal ice formations, which either formed by the: (1) freezing of dripping water (ice stalagmite and stalactite); (2) freezing of stagnant or slow moving water (floor ice and curtain ice) and; (3) condensation of water vapor (hoar ice), all (except floor ice) showed kinetic isotope effects associated with the rapid freezing of calcium bicarbonate water. This was made evident in the dD, d18 O and d (deuterium excess) compositions of the formed ice where they plot along a kinetic freezing line. The cryogenic calcite powders, which are found on the surface of the seasonal ice formations, also show kinetic isotope effects. Their d13 C and d18 O values are among the highest measured in cold-climate carbonates and are caused by the rapid rate of freezing, which results in strong C-O disequilibrium between the water, dissolved C species in the water, and precipitating calcite. Although the cryogenic calcite precipitated as powders, diverse crystal habits were observed under scanning electron microscope, which included rhombs, aggregated rhombs, spheres, needles, and aggregated structures. The rhomb crystal habits were observed in samples stored and observed at room temperature, whereas the sphere and needle structures were observed in the samples kept and observed under cryogenic conditions. Considering that the formation of cryogenic calcite is purely abiotic (freezing of calcium bicarbonate water), the presence of spherical structures, commonly associated with biotic processes, might represent vaterite, a polymorph of calcite stable only at low temperatures. It is therefore suggested that care should be taken before suggesting biological origin to calcite precipitates based solely on crystal habits because they might represent pseudo-biogenic structures formed through abiotic processes.

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