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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 habitat is the immediate surroundings (living place) of a plant or animal; everything necessary to life in a particular location except the organism itself [23].?

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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 geochemical modeling (Keyword) returned 15 results for the whole karstbase:
Showing 1 to 15 of 15
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

Changes in the isotopic and chemical composition of ground water resulting from a recharge pulse from a sinking stream, 1998, Katz B. G. , Catches J. S. , Bullen T. D. , Michel R. L. ,
The Little River, an ephemeral stream that drains a watershed of approximately ss km(2) in northern Florida, disappears into a series of sinkholes along the Cody Scarp and flows directly into the carbonate Upper Floridan aquifer, the source of water supply in northern Florida. The changes in the geochemistry of ground water caused by a major recharge pulse from the sinking stream were investigated using chemical and isotopic tracers and mass-balance modeling techniques, Nine monitoring wells were installed open to the uppermost part of the aquifer in areas near the sinks where numerous subterranean karst solution features were identified using ground penetrating radar. During high-flow conditions in the Little River, the chemistry of water in some of the monitoring wells changed, reflecting the mixing of river water with ground water. Rapid recharge of river water into some parts of the aquifer during high-flow conditions was indicated by enriched values of delta O-18 and delta deuterium (-1.67 to -3.17 per mil and -9.2 to -15.6 per mil, respectively), elevated concentrations of tannic acid, higher (more radiogenic) Sr-87/Sr-86 ratios, and lower concentrations of Rn-222, silica, and alkalinity compared to low-how conditions. The proportion of river water that mixed with ground water ranged from 0.10 to 0.67 based on binary mixing models using the tracers O-18, deuterium, tannic acid, silica, Rn-222, and Sr-87/Sr-86. On the basis of mass-balance modeling during steady-state how conditions, the dominant processes controlling carbon cycling in ground water are the dissolution of calcite and dolomite in aquifer material, and aerobic degradation of organic matter. (C) 1998 Elsevier Science B.V. All rights reserved

Processes controlling colloid composition in a fractured and karstic aquifer in eastern Tennessee, USA, 1998, Mccarthy J. F. , Shevenell L. ,
Groundwater was sampled from a number of wells along recharge pathways between fractured shale and karstic formations to evaluate the chemical and hydrologic mechanisms controlling the nature and abundance of groundwater colloids. The colloids recovered using low flow rate purging and sampling exhibited a composition and abundance consistent with lithology, flow paths, and effects of hydrology and aqueous chemistry on colloid mobilization and stability. In general, the larger-size colloids and Ca-containing colloids were more abundant in the karstic lithologies, while Na-containing colloids were more important in the shales. The composition of the colloids reflected recharge pathways from the fractured shale and dolomite formations on the ridges into the limestone in the valley floor. The Mg-colloids in the limestone reflect the possible contributions from the dolomite, while the Na, K, and Si reflect possible contributions from the shale, However, it was not possible to use the colloid composition as a signature to demonstrate colloid transport from one lithology to another. Mixing of recharge water from the shale with groundwater within the limestone formation and precipitation/dissolution reactions could account for the colloids present in the limestone without invoking transport of specific shale-derived colloids into the limestone formation. The abundance of colloids in groundwater appears to be controlled by both chemical factors affecting colloid stability, as well as physical factors related to hydrology (storm-driven recharge and water velocities). In general, colloids were more abundant in wells with low ionic strength, such as shallow wells in water table aquifers near sources of recharge at the top of the ridges, Increases in cation concentrations due to dissolution reactions along Bow paths were associated with decreases in colloid abundance. However, in spite of elevated ionic strength, colloid concentrations tended to be unexpectedly high in karstic wells that were completed in cavities or water-bearing fractures. The higher levels of colloids appear to be related to storm-driven changes in chemistry or flow rates that causes resuspension of colloids settled within cavities and fractures. Published by Elsevier Science B.V

Geochemical modeling of groundwater in karst area and its application at Pingdingshan coalfield, 1998, Wang G. C. , Tao S. , Shen Z. L. , Zhong Z. X. ,
Several approaches including hydrogeochemistry and isotope hydrogeology have been used to investigate the karst groundwater systems at Pingdingshan coalfield in recent years. The results of the modeling and evaluation of groundwater chemistry, as parts of recent research progress at the area, are presented. The characteristics of Cambrian karst groundwater flow was analyzed in terms of tritium distribution of groundwater based on the fact that the Guodishan fault, the largest one within the coalfield, is divided into permeable (southern and northern) and impermeable (middle) sections. The evolution of groundwater chemistry, the suitability of geothermometers and the feature of karst development were deduced and discussed using the speciation modeling and mass balance approach

Geostatistical and geochemical analysis of surface water leakage into groundwater on a regional scale: a case study in the Liulin karst system, northwestern China, 2001, Wang Y. , Ma T. , Luo Z. ,
The Liulin karst system is typical of hydrogeological systems in northern China, with a group of springs as the dominant way of regional groundwater discharge. Surface water leakage into groundwater has been observed in six sections of the rivers in the study area. To extract hydrogeological information from hydrochemical data, 29 water samples were collected from the system. On a trilinear diagram, most of the groundwater samples are clustered around the surface waters, indicating the effect of leakage on their chemistry. R-mode factor analysis was made on seven variables (Na, Ca, Mg, SO4, Cl, HCO3, and NO3) of the samples and three principal factors were obtained: the F-1 factor is composed of Ca, Mg and SO4, the F-2 of HCO3 and NO3, and the F-3 of Na and Cl. These factors are then used as regionalized variables in ordinary Kriging for unbiased estimates of the spatial variations of their scores. Considering regional hydrogeological conditions, the hydrogeological implications of the spatial distribution of the factor scores as related to the effects of the surface leakage are discussed. To evaluate the geochemical processes, the geochemical modeling code NETPATH was employed. The modeling results: show that mixing commonly occurs in the system and dolomite dissolution is more important than calcite dissolution. Dedolomitization (calcite precipitation and dolomite dissolution driven by anhydrite dissolution) is locally important, in the western flank of the system where the surface water leakage has the least effect.

Trace element (Th, U, Pb, REE) behaviour in a cryptokarstic halloysite and kaolinite deposit from Southern Belgium: importance of 'accessory' mineral formation for radioactive pollutant trapping, 2002, De Putter T, Andre L, Bernard A, Dupuis C, Jedwab J, Nicaise D, Perruchot A,
Hectometer wide cryptokarsts in Paleozoic limestone from Southern Belgium have been studied, to determine to what extent U, Th, Ph and rare earth elements (REE) have been mobilized in the karst sedimentary filling, during a Miocene weathering event. The weathering process resulted in the massive halloysite/kaolinite formation at the karst wall. As with most fossil systems, data on weathering fluid chemistry are lacking, hence it is difficult to quantify relevant parameters such as pH, Eh, and to address solution chemistry. However, on the basis of both field studies of more recent systems, and of geochemical modeling, it is proposed that moderately acid fluids percolated through a multi-layer sedimentary filling, in near-surface conditions and in a temperate/warm climate. Special attention is paid to the trace element immobilization/trapping processes, in newly crystallized REE phosphates, at the karst wall. Analytical methods used include major/trace element geochemistry (emission ICP, ICP-MS) and mineralogy (XRD, SEM, TEM, microprobe). The results suggest that both the sandy sediments that are in contact with the karst carbonate wall, and the carbonate wall itself acted as a kind of geochemical 'barrier'. Mineralization cells settled there, at the decimeter to meter scale. This results in sequential trace element (Pb, Th, REE, U) trapping, according to the affinity of these elements for the aqueous solution. At the end of the sequence, minute U-rich automorphic (Ce, Nd) monazite crystals (from 3 nm upwards) formed on kaolinite flakes. Though the analogy between the studied cryptokarst and planned surface-based repositories for low-level radioactive waste (LLW) in argillaceous context is far from complete, the results outlined here are relevant because they show that even in natural-i.e. intrinsically uncontrolled and unmonitored-systems, 'pollutant' radionuclide (U, Th, REE, Pb) migration paths are often limited in space. Various processes converge towards trapping of these elements, that are present in the radioactive waste. (C) 2002 Elsevier Science Ltd. All rights reserved

Formation of Willemite in Hydrothermal Environments, 2003, Brugger J, Mcphail Dc, Wallace M, Waters J,
Willemite (zinc silicate) is the main zinc mineral in some carbonate-hosted ore deposits (e.g., Franklin, New Jersey; Vazante, Brazil; Beltana, South Australia; Kabwe, Zambia). Recent interest in these unconventional zinc deposits has increased because of high zinc grades that exceed 40 wt percent, relatively low environmental impact of ore processing owing to the lack of acid-generating sulfides in the waste, and advances in ore processing technologies. In the past, most metallogenic studies proposed formation of willemite deposits by supergene or hypogene alteration of preexisting sulfide deposits. However, recent data on the Vazante, Beltana, and Kabwe deposits indicate willemite crystallization at temperatures in excess of 150{degrees}C, raising the possibility of primary precipitation from hydrothermal fluids. We use numerical geochemical modeling to examine the formation of willemite under hydrothermal conditions. Activity-activity diagrams reveal that, in the presence of dissolved sulfur and quartz, willemite instead of sphalerite will precipitate under oxidizing (e.g., hematite-stable, sulfate-predominant) and alkaline (pH higher than K feldspar-muscovite-quartz) conditions. Willemite also becomes more stable, relative to sphalerite, at high temperature, and willemite can coexist with magnetite at 300{degrees}C. The stabilities and solubilities of sphalerite, willemite, smithsonite, hydrozincite, and zincite were calculated for wide ranges of temperature (25{degrees}-300{degrees}C), chloride concentration, dissolved sulfur and carbon concentrations, pH, quartz saturation, and oxidation potential. Plots of the solubility of the different minerals as a function of two variables (e.g., temperature and redox state; pH and redox state) allow us to predict the effects of changing chemical conditions, which in turn permits an estimate of the efficiency of particular precipitation processes. Cooling is an effective process for precipitating sphalerite but not willemite, whereas pH increase (e.g., by acidic fluids reacting with carbonates) is effective for precipitating willemite but not sphalerite. Dynamic geochemical models that simulate physicochemical processes are used to understand the formation of the Beltana willemite deposit in the Adelaide geosyncline of South Australia. This small, high grade deposit (850,000 t at 36% Zn) is hosted in dolomite of the Cambrian Ajax Limestone, next to a tectonic contact with the diapiric, halite-bearing clastic sediments of the Callanna Group. The orebody is associated with hematite alteration and is characterized by the total absence of sulfides; willemite is the only zinc ore mineral, and the arsenate hedyphane (Ca2Pb3[AsO4]3Cl) is the main lead mineral. The model results show that willemite will precipitate in response to water-rock interaction and fluid mixing processes at temperatures above 120{degrees}C. The presence of arsenate in the hydrothermal fluid is likely to have been important at Beltana; in arsenate-absent models sulfate is reduced to sulfide by the precipitation of ferrous iron as hematite, resulting in the precipitation of sphalerite and galena. In contrast, in models including arsenate the reduction of sulfate to sulfide is inhibited and willemite is predicted to precipitate

Role of fluid mixing in deep dissolution of carbonates, 2003,

The presence of cavities filled with new minerals in carbonate rocks is a common feature in oil reservoirs and lead-zinc deposits. Since groundwater equilibrates rapidly with carbonates, the presence of dissolution cavities in deep carbonate host rocks is a paradox. Two alternative geochemical processes have been proposed to dissolve carbonates at depth: hydrogen sulfide oxidation to sulfuric acid, and metal sulfide precipitation. With the aid of geochemical modeling we show that mixing two warm solutions saturated with carbonate results in a new solution that dissolves limestone. Variations in the proportion of the end-member fluids can also form a supersaturated mixture and fill the cavity with a new generation of carbonate. Mixing is in general more effective in dissolving carbonates than the aforementioned processes. Moreover, mixing is consistent with the wide set of textures and mineral proportions observed in cavity infillings


Strontium isotope characterization and major ion geochemistry of karst water flow, Shentou, northern China, 2006, Wang Yanxin, Guo Qinghai, Su Chunli, Ma Teng,
SummaryKarst water is the most important source of water supply for Shanxi province, northern China. The Shentou springs are representative of the 19 major karst springs at Shanxi. The total area of the Shentou karst water system is 5316 km2, the Middle Ordovician limestone being its major karst aquifer. In this study, data about the strontium isotope geochemistry and major ion hydrochemistry were analyzed to understand the flow patterns and hydrogeochemical processes of karst water at Shentou. The contour map of TDS value of karst water and that of Sr concentration are similar, showing the general tendency of increase from the northern, western and southern boundary to the discharge area. The average values of 87Sr/86Sr ratios of karst water decrease from recharge (0.7107) to discharge area (0.7102), evolving towards those of limestone hostrocks. Comparison of 87Sr/86Sr ratios with Sr content suggests that isotopic compositions of some karst water samples from the recharge and flow through area should be the result of interaction between aquifer limestone matrix and strontium-poor recharge waters of meteoric origin. However, for samples from the discharge area that are plotted above the mixing line, mixing with groundwater in the Quaternary aquifers with high 87Sr/86Sr ratios may be another factor controlling Sr isotope chemistry. Two major groundwater flow paths were discerned from hydrogeological and geochemical data. Along both flow paths, the 87Sr/86Sr ratios of karst water show a general tendency of decrease. Geochemical modeling of the major ion geochemistry of karst water using PHREEQC also indicates that the chemistry of springs should be affected by the incorporation of groundwater in Quaternary aquifer. The effect of the mixing action on the spring hydrochemistry in flow path 1 is more remarkable than that in flow path 2, according to different mixing ratios in both paths (30% in flow path 1 and 5% in flow path 2)

Unusual Phosphate Concretions Related to Groundwater Flow in a Continental Environment, 2006, Thiry Medard, Galbois Jean, Schmitt Jean Michel,
Occurrence of phosphate cemented-sandstone concretions in alluvial sand containing archaeological layers implies that they have formed during the last 2000 years. Morphology and petrography of the concretions indicates a relationship with groundwater cementation. The phosphate cement of the concretions consists of concentric isopachous aureoles, about 10 {micro}m thick, that wrap the detrital grains. Aureoles are formed of collophane, the cryptocrystalline or amorphous variety of hydroxyapatite. Geochemical modeling indicates that the apatite cement likely results from the leaching of a preexisting phosphate deposit (bones?) in an acidic soil environment and the precipitation of dissolved phosphate under pH control at the mixing zone of down-moving soil-water with the calcite-saturated groundwater

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs, 2006, Toth D. J. , Katz B. G.

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO3 (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca– HCO3 spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquiferwater with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (3H), helium- 3 (3Hetrit), sulfur hexafluoride (SF6)—for four Ca–HCO3 spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.


Potential environmental issues of C02 storage in deep saline aquifers: Geochemical results from the Frio-1 Brine Pilot test, Texas, USA, 2009, Kharaka Y. K. , Thordsena J. , Hovorkab S. D. , Nanceb H. S. , Colee D. R. , Phelps T. J. , Knauss K. G.

Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic C02 that must be sequestered to mitigate global wanning and related climate changes. To investigate the potential for the long-term storage of C02 in such aquifers, 1600 t of C02 were injected at 1500 m depth into a 24-m-thick "C" sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast Fluid samples obtained before C02 injection from the injection well and an observation well 30 m updip showed a Na-ca-a type brine with ~93,000 mg/L IDS at saturation with CH.t at reservoir conditions; gas analyses showed that CH.t comprised ~95% of dissolved gas, but C02 was low at 0.3%. Following C02 breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5-5.7), pronounced increases in alkalinity (100-3000 mgfL as HC03) and in Fe (30-1100 mgfL), a slug of very high DOC values, and significant shifts in the isotopic compositions of H20, DIC, and CH.t. These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ~3.0 at subsurface conditions) of the brine in contact with supercritical C~. These geochemical parameters, together with perfluorocarbon tracer gases (PFrs), were used to monitor migration of the injected C02 into the overlying Frio "B", composed of a 4-m-thick sandstone and separated from the "C" by ~ts m of shale and siltstone beds. Results obtained from the Frio "B" 6 months after injection gave chemical and isotopic markers that show significant ~ (2.9% compared with 0.3% C02 in dissolved gas) migration into the "B" sandstone. Results of samples collected 15 months after injection, however, are ambiguous, and can be interpreted to show no additional injected C02 in the "B" sandstone. The presence of injected C02 may indicate migration from "C" to "B" through the intervening beds or, more likely, a short-term leakage through the remedial cement around the casing of a 50-year old well. Results obtained to date from four shallow monitoring groundwater wells show no brine or C02 leakage through the Anahuac Formation, the regional cap rock.


Computational Investigation of Fundamental Mechanisms Contributing to Fracture Dissolution and the Evolution of Hypogene Karst Systems, 2011, Chaudhuri A. , Rajaram H. , Viswanathan H. S. , Zyvoloski G. , Stauffer P. H.

Hypogene karst systems evolve by dissolution resulting from the cooling of water flowing upward against the geothermal gradient in limestone formations. We present a comprehensive coupled-process model of fluid flow, heat transfer, reactive transport and buoyancy effects to investigate the origin of hypogene karst systems by fracture dissolution. Our model incorporates the temperature and pressure dependence of the solubility and dissolution kinetics of calcite. Our formulation inherently incorporates mechanisms such as “mixing corrosion” that have been implicated in the formation of hypogene cave systems. It also allows for rigorous representation of temperature-dependent fluid density and its consequences at various stages of karstification. The model is applied to investigate karstification over geological time scales in a network of faults/fractures that serves as a vertical conduit for upward flow. We considered two different conceptual hydrogeologic models. In the first model, the upward flow is controlled by a constant pressure gradient. In the second model, the flow is induced by topographic effects in a mountainous hydrologic system. During the very early stages of fracture growth, there is a positive feedback between fluid flow rate, heat transfer and dissolution. In this stage the dissolution rate is largely controlled by the retrograde solubility of calcite and aperture growth occurs throughout the fracture. For the first model, there is a period of slow continuous increase in the mass flow rate through the fracture, which is followed by an abrupt rapid increase. We refer to the time when this rapid increase occurs as the maturation time. For the second model of a mountainous hydrologic system, the fluid flux through the fracture remains nearly constant even though the fracture permeability and aperture increase. This is largely because the permeability of the country rock does not increase significantly. While this limits the fluid flux through the system, it does not impede karstification. At later stages, forced convection and buoyant convection effects arise in both models due to the increased permeability of the evolving fracture system. Our results suggest that there is s strong tendency for buoyant convection cells to form under a wide range of conditions. A modified Rayleigh number provides a unified quantitative criterion for the onset of buoyant convection across all cases considered. Once buoyant convection cells are set up, dissolution is sustained in the upward flow portions of the cells, while precipitation occurs in the regions of downward flow. We discuss the implications of this type of flow pattern for the formation of hot springs and mazework caves, both of which are characteristic of hypogene karst environments. We also investigate the sensitivity of karst evolution to various physical and geochemical factors.


Biological Control on Acid Generation at the Conduit-Bedrock Boundary in Submerged Caves: Quantification through Geochemical Modeling, 2013, Herman Janet S. , Hounshell Alexandria G. , Franklin Rima B, Mills Aaron L.

No-mount Cave, located in wekiwa Springs State Park in central Florida, USA, is an aphotic, submerged, freshwater cave in which large colonies of sulfur-oxidizing bacteria live in filamentous microbial mats. Upwardly discharging groundwater enters the cave from the Upper Floridan aquifer, specifically the Eocene-aged Ocala Limestone. we undertook a combined field, laboratory, and modeling study in which we sought to determine the amount of calcite dissolution attributable to the generation of protons by microbially mediated sulfide oxidation. The chemical compositions of groundwater within the limestone formation collected through a newly designed sampling device and of water in the cave conduit were used in geochemical modeling. we used the reaction-path model PHREEqCI to quantify the amount of calcite dissolution expected under various plausible scenarios for mixing of formation water with conduit water and extent of bacterial sulfide oxidation. Laboratory experiments were conducted using flow-through columns packed with crushed limestone from the study site. Replicate columns were eluted with artificial groundwater containing dissolved HS- in the absence of microbial growth. without biologically mediated sulfide oxidation, no measurable calcite dissolution occurred in laboratory experiments and no additional amount of speleogenesis is expected as formation water mixes with conduit water in the field. In contrast, significant calcite dissolution is driven by the protons released in the biological transformation of the aqueous sulfur species. Although a range of results were calculated, a plausible amount of 158 mg Ca2+ released to conduit water per liter of groundwater crossing the formation-conduit boundary and mixing with an equal volume of conduit water was predicted. Our modeling results indicate that significant cave development can be driven by microbially mediated sulfide oxidation under these hydrogeochemical conditions


Early-stage hypogene karstification in a mountain hydrologic system: A coupled thermohydrochemical model incorporating buoyant convection, 2013, Chaudhuri A. , Rajaram H. , Viswanathan H

The early stage of hypogene karstification is investigated using a coupled thermohydrochemical model of a mountain hydrologic system, in which water enters along a water table and descends to significant depth (_1 km) before ascending through a central high-permeability fracture. The model incorporates reactive alteration driven by dissolution/ precipitation of limestone in a carbonic acid system, due to both temperature- and pressuredependent solubility, and kinetics. Simulations were carried out for homogeneous and heterogeneous initial fracture aperture fields, using the FEHM (Finite Element Heat and Mass Transfer) code. Initially, retrograde solubility is the dominant mechanism of fracture aperture growth. As the fracture transmissivity increases, a critical Rayleigh number value is exceeded at some stage. Buoyant convection is then initiated and controls the evolution of the system thereafter. For an initially homogeneous fracture aperture field, deep well-organized buoyant convection rolls form. For initially heterogeneous aperture fields, preferential flow suppresses large buoyant convection rolls, although a large number of smaller rolls form. Even after the onset of buoyant convection, dissolution in the fracture is sustained along upward flow paths by retrograde solubility and by additional ‘‘mixing corrosion’’ effects closer to the surface. Aperture growth patterns in the fracture are very different from those observed in simulations of epigenic karst systems, and retain imprints of both buoyant convection and preferential flow. Both retrograde solubility and buoyant convection contribute to these differences. The paper demonstrates the potential value of coupled models as tools for understanding the evolution and behavior of hypogene karst systems.


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