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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 half-exposed karren is these are patches of soil on otherwise bare limestone that attack the rock by means of biogenic co2 [3].?

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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 geologically relevant situations (Keyword) returned 21 results for the whole karstbase:
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THE KINETICS OF CALCITE DISSOLUTION AND PRECIPITATION IN GEOLOGICALLY RELEVANT SITUATIONS OF KARST AREAS .1. OPEN SYSTEM, 1985, Buhmann D, Dreybrodt W,

ORIGIN AND MORPHOLOGY OF LIMESTONE CAVES, 1991, Palmer A. N. ,
Limestone caves form along ground-water paths of greatest discharge and solutional aggressiveness. Flow routes that acquire increasing discharge accelerate in growth, while others languish with negligible growth. As discharge increases, a maximum rate of wall retreat is approached, typically about 0.01-0.1 cm/yr, determined by chemical kinetics but nearly unaffected by further increase in discharge. The time required to reach the maximum rate is nearly independent of kinetics and varies directly with flow distance and temperature and inversely with initial fracture width, discharge, gradient, and P(CO2). Most caves require 10(4) - 10(5) yr to reach traversable size. Their patterns depend on the mode of ground-water recharge. Sinkhole recharge forms branching caves with tributaries that join downstream as higher-order passages. Maze caves form where (1) steep gradients and great undersaturation allow many alternate paths to enlarge at similar rates or (2) discharge or renewal of undersaturation is uniform along many alternate routes. Flood water can form angular networks in fractured rock, anastomotic mazes along low-angle partings, or spongework where intergranular pores are dominant. Diffuse recharge also forms networks and spongework, often aided by mixing of chemically different waters. Ramiform caves, with sequential outward branches, are formed mainly by rising thermal or H2S-rich water. Dissolution rates in cooling water increase with discharge, CO2 content, temperature, and thermal gradient, but only at thermal gradients of more than 0.01-degrees-C/m can normal ground-water CO2 form caves without the aid of hypogenic acids or mixing. Artesian flow has no inherent tendency to form maze caves. Geologic structure and stratigraphy influence cave orientation and extent, but alone they do not determine branch-work versus maze character

DISSOLUTION OF ARAGONITE-STRONTIANITE SOLID-SOLUTIONS IN NONSTOICHIOMETRIC SR(HCO3)2-CA(HCO3)2-CO2-H2O SOLUTIONS, 1992, Plummer L. N. , Busenberg E. , Glynn P. D. , Blum A. E. ,
Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated nonstoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25-degrees-C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer approximately 60 angstrom on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer approximately 25 angstrom (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a nonstoichiometric surface reactive zone significantly decreases dissolution rates

EARLY DEVELOPMENT OF KARST SYSTEMS .1. PREFERENTIAL FLOW PATH ENLARGEMENT UNDER LAMINAR-FLOW, 1994, Groves C. G. , Howard A. D. ,
Modeling of flow and solutional processes within networks of interconnected conduits in limestone aquifers indicates that enlargement occurs very selectively during the early stages of karst aquifer development under laminar flow. If initial flow paths are uniform in size, almost all enlargement occurs along a single set of connected conduits that lie along a direct path between recharge and discharge locations and are aligned along the hydraulic gradient. With a sufficiently large variation in initial aperture widths, enlargement occurs along the flow path offering the least resistance to flow, but since flow rates in laminar flow are proportional to the fourth power of diameter but only linearly proportional to hydraulic gradient, the preferentially enlarged set of fractures may follow an indirect path. Results disfavor earlier suggestions that nonselective cave patterns result from artesian flows (at least under laminar flow conditions) and that all passages should be competitive until the onset of turbulent flow

Recent flowstone growth rates: field measurements and comparison to theoretical results, 1995, Baker A. , Smart Pl. ,
The model of calcite precipitation kinetics of D. Buhmann and W. Dreybrodt, based on the rate laws of L.N. Plummer et al., is used to predict cave flowstone growth rates. These theoretically modelled growth rates are compared to actual growth rates of recent samples found in cave and mine sites in southwest England. A good agreement is found between modelled and actual growth rates within the 95% confidence level of the determinations, although in general modelled growth rates overestimate actual growth rate by between 2.4 and 4.7 times. Several reasons for this overestimation are discussed, including uncertainties arising from the experimental data of L.N. Plummer et al., seasonal shut-off of water flow onto the flowstones and significant variations in the growth rate determining parameters during the period of flowstone growth. For one flowstone an underestimation of growth rate is observed and is explained by the presence of rimstone pools which pond water on the sample surface

HYDRODYNAMIC CONTROL OF INORGANIC CALCITE PRECIPITATION IN HUANGLONG RAVINE, CHINA - FIELD-MEASUREMENTS AND THEORETICAL PREDICTION OF DEPOSITION RATES, 1995, Liu Z. H. , Svensson U. , Dreybrodt W. , Yuan D. X. , Buhmann D. ,
Hydrochemical and hydrodynamical investigations are presented to explain tufa deposition rates along the flow path of the Huanglong Ravine, located in northwestern Sichuan province, China, on an altitude of about 3400 m asl. Due to outgassing of CO2 the mainly spring-fed stream exhibits, along a valley of 3.5 km, calcite precipitation rates up to a few mm/year. We have carried out in situ experiments to measure calcite deposition rates at rimstone dams, inside of pools and in the stream-bed. Simultaneously, the downstream evolution of water chemistry was investigated at nine locations with respect to Ca2 Mg2, Na, Cl-, SO42-, and alkalinity. Temperature, pH, and conductivity were measured in situ, while total hardness, Ca-T, and alkalinity have been determined immediately after sampling, performing standard titration methods. The water turned out to be of an almost pure Ca-Mg-HCO3 type. The degassing of CO2 causes high supersaturation with respect to calcite and due to calcite precipitation the Ca2 concentration decreases from 6 . 10(-3) mole/l upstream down to 2.5 . 10(-3) mole/l at the lower course. Small rectangular shaped tablets of pure marble were mounted under different flow regimes, i.e., at the dam sites with fast water flow as well as inside pools with still water. After the substrate samples had stayed in the water for a period of a few days, the deposition rates were measured by weight increase, up to several tens of milligrams. Although there were no differences in hydrochemistry, deposition rates in fast flowing water were higher by as much as a factor of four compared to still water, indicating a strong influence of hydrodynamics. While upstream rates amounted up to 5 mm/year, lower rates of about 1 mm/year were observed downstream. Inspection of the marble substrate surfaces by EDAX and SEM (scanning electron microscope) revealed authigeneously grown calcite crystals of about 10 mu m. Their shape and habit are indicative of a chemically controlled inorganic origin. By applying a mass transfer model for calcite precipitation taking into account the reaction rates at the surface given by Plummer et al. (1978), slow conversion of CO2 into H and HCO3-, and diffusional mass transport across a diffusion boundary layer, we have calculated the deposition rates from the hydrochemistry of the corresponding locations. The calculated rates agree within a factor of two with the experimental results. Our findings confirm former conclusions with respect to fast flow conditions: reasonable rates of calcite precipitation can be estimated in reducing the PWP-rate calculated from the chemical composition of the water by a factor of about ten, thus correcting for the influence of the diffusion boundary layer

The kinetics of the reaction CO2?>H? as one of the rate limiting steps for the dissolution of calcite in the system H2O-CO2-CaCO3, 1996, Dreybrodt W, Lauckner J, Liu Zh, Svensson U, Buhmann D,
Dissolution of CaCO3 in the system H2O-CO2-CaCO3 is controlled by three rate-determining processes: The kinetics of dissolution at the mineral surface, mass transport by diffusion, and the slow kinetics of the reaction H2O CO2 = H HCO3-. A theoretical model of Buhmann and Dreybrodt (1985a,b) predicts that the dissolution rates depend critically on the ratio V/A of the volume V of the solution and the surface area A of the reacting mineral. Experimental data verifying these predictions for stagnant solutions have been already obtained in the range 0.01 cm < V/A < 0.1 cm. We have performed measurements of dissolution rates in a porous medium of sized CaCO3 particles for V/A in the range of 2 . 10(-4) cm and 0.01 cm in a system closed with respect to CO2 using solutions pre-equilibrated with an initial partial pressure of CO2 of 1 . 10(-2) and 5 . 10(-2) atm. The results are in satisfactory agreement with the theoretical predictions and show that especially for V/A < 10(-3) cm dissolution is controlled entirely by conversion of CO2 into H and HCO3-, whereas in the range from 10(-3) cm up to 10(-1) cm both CO2-conversion and molecular diffusion are the rate controlling processes. This is corroborated by performing dissolution experiments using 0.6 mu molar solutions of carbonic anhydrase, an enzyme enhancing the CO2-conversion rates by several orders of magnitude. In these experiments CO2 conversion is no longer rate limiting and consequently the dissolution rates of CaCO3 increase significantly. We have also performed batch experiments at various initial pressures of CO2 by stirring sized calcite particles in a solution with V/A = 0.6 cm and V/A = 0.038 cm. These data also clearly show the influence of CO2-conversion on the dissolution rates. In all experiments inhibition of dissolution occurs close to equilibrium. Therefore, the theoretical predictions are valid for concentrations c less than or equal to 0.9 c(eq). Summarising we find good agreement between experimental and theoretically predicted dissolution rates. Therefore, the theoretical model can be used with confidence to find reliable dissolution rates from the chemical composition of a solution for a wide field of geological applications

Principles of early development of karst conduits under natural and man-made conditions revealed by mathematical analysis of numerical models, 1996, Dreybrodt W,
Numerical models of the enlargement of primary fissures in limestone by calcite aggressive water show a complex behavior. If the lengths of the fractures are large and hydraulic heads are low, as is the case in nature, dissolution rates at the exit of the channel determine its development by causing a slow increase of water flow, which after a long gestation time by positive feedback accelerates dramatically within a short time span. Mathematical analysis of simplified approximations yields an analytical expression for the breakthrough time, when this happens, in excellent agreement with the results of a numerical model. This expression quantifies the geometrical, hydraulic, and chemical parameters determining such karat processes. If the lengths of the enlarging channels are small, but hydraulic heads are high, as is the case for artificial hydraulic structures such as darns, it is the widening at the entrance of the flow path which determines the enlargement of the conduit. Within the lifetime of the dam this can cause serious water losses, This can also be explained by mathematical analysis of simplified approximations which yield an analytical threshold condition from which the safety of a dam can be judged. Thus in both cases the dynamic processes of karstification are revealed to gain a deeper understanding of the early development of karst systems. As a further important result, one finds that minimum conditions, below which karstification cannot develop, do not exist

The effect of metal cations on the kinetics of limestone neutralisation of acid waters, 1997, Vantonder G. J. , Schutte C. F. ,
Limestone (CaCO3), is a lower cost alternative to lime (CaO) for the neutralisation of acid water, but the limestone neutralisation reaction is impaired by iron(II), iron(III) and aluminium in solution. This paper describes the kinetics of limestone neutralisation in the presence of these metals. The reaction rate is affected by the type of metal cation, by the concentration of the cation and by pH. At pH levels below 2.0 the limestone dissolution reaction rate decreases sharply with increasing pH. In the pH range 4.0 to 5.5 the reaction rate decreases linearly with increasing pH. The pH range 2.0 to 4.0 is a transition range, from the non-linear to linear dissolution rate characteristics. Metal concentrations below 80 mg l(-1): At pH levels less than 4, iron(II) had the strongest suppressing effect followed by aluminium, while the presence of iron(III) increased the reaction rate. In the pH range 4.0 to 5.5 aluminium had the strongest suppressing effect followed by iron(III) and iron(II). Metal concentrations above 80 mg l(-1): Iron(II) and aluminium suppress the reaction rate at all pH levels. At pH levels less than 4 iron(II) had the strongest suppressing effect, followed by aluminium. In the pH range 4.0 to 5.5 aluminium had the strongest suppressing effect followed by iron(II). With iron(III) the rate is suppressed at pH levels below 2, however the rate is speeded up in the pH range 25 to 3.5. At higher pH levels, the iron(III) concentration is limited to less than 80 mg l(-1) because of precipitation of iron(III) at pH levels higher than 2.5. The extent to which the overall neutralisation reaction proceeds was modelled to assist in reactor design. The overall reaction is impaired most by aluminium, followed by iron(II) and iron(III)

Precipitation kinetics of calcite in the system CaCO3-H2O-CO2: The conversion to CO2 by the slow process H?->CO2? as a rate limiting step, 1997, Dreybrodt W, Eisenlohr L, Madry B, Ringer S,
Precipitation rates of CaCO3 from supersaturated solutions in the H2O - CO2 - CaCO3 system are controlled by three rate-determining processes: the kinetics of precipitation at the mineral surface, mass transport of the reaction species involved to and from the mineral surface, and the slow kinetics of the overall reaction HCO3- H --> CO2 H2O. A theoretical model by Buhmann and Dreybrodt (1985a,b) taking these processes into account predicts that, due to the slow kinetics of this reaction, precipitation rates to the surface of CaCO3 minerals depend critically on the ratio V/A of the volume V of the solution to the surface area A of the mineral in contact with it, for both laminar and turbulent flow. We have performed measurements of precipitation rates in a porous medium of sized particles of marble, limestone, and synthetic calcite, with V/A ratios ranging from 3.10(-4) to 1.2-10(-2) cm at 10 degrees C. Calcite was precipitated from supersaturated solutions with [Ca2] approximate to 4 mmol/L and an initial P-CO2 of 5.10(-3) or 1.10(-3) atm, respectively, using experimental conditions which prevented exchange of CO2 with the atmosphere, i.e., closed system. The results are in qualitative agreement with the theoretical predictions. Agreement with the observed data, however, is obtained by modifying the rate law of Plummer et al. (1978) to take into account surface-controlled inhibition effects. Experiments with supersaturated solutions containing carbonic anhydrase, an enzyme which enhances the conversion of HCO3- into CO2, yield rates increased by a factor of up to 15. This provides for the first time unambiguous experimental evidence that this reaction is rate limiting. We have also measured precipitation rates in batch experiments, stirring sized mineral particles in a solution with V/A ranging from 0.03 to 0.75 cm. These experiments also give clear evidence on the importance of the conversion of HCO3- into CO2 as rate limiting step. Taken together our experiments provide evidence that the theoretical model of Buhmann and Dreybrodt (1985a,b) can be used to predict reliable rates from the composition of CaHCO3- solutions with low ionic strength in many geologically relevant situations. Copyright (C) 1997 Elsevier Science Ltd

An experimental study of calcite and limestone dissolution rates as a function of pH from -1 to 3 and temperature from 25 to 80 degrees C, 1998, Alkattan M, Oelkers Eh, Dandurand Jl, Schott J,
Dissolution rates of single calcite crystals, limestones, and compressed calcite powders were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed in aqueous HCl solutions over the bulk solution pH range -1 to 3, and at temperatures of 25 degrees, 50 degrees, and 80 degrees C. Corresponding rates of the three different sample types are identical within experimental uncertainty. Interpretation of these data using equations reported by Gregory and Riddiford [Gregory, D.P., Riddiford, A.C., 1956. Transport to the surface of a rotating disc. J. Chem. Sec. London 3, 3756-3764] yields apparent rate constants and H diffusion coefficients. The logarithms of overall calcite dissolution rates (r) obtained at constant disk rotation speed are inversely proportional to the bulk solution pH, consistent with r = k(2') a(H,b), where k(2)' stands for an apparent rate constant and a(H,b) designates the hydrogen ion activity in the bulk solution, This variation of dissolution rates with pH is consistent with corresponding rates reported in the literature and the calcite dissolution mechanism reported by Wollast [Wollast, R., 1990. Rate and mechanism of dissolution of carbonates in the system CaCO3-MgCO3. In: Stumm, W. (Ed.), Aquatic Chemical Kinetics. Wiley, pp. 431-445]. Apparent rate constants for a disk rotation speed of 340 rpm increase from 0.07 0.02 to 0.25 0.02 mol m(-2) s(-1) in response to increasing temperature from 25 degrees to 80 degrees C. H diffusion coefficients increase from (2.9 to 9.2) x 10(-9) m(2) s(-1) over this temperature range with an apparent activation energy of 19 kJ mol(-1). (C) 1998 Elsevier Science B.V. All rights reserved

Kinetics and mechanisms of precipitation of calcite as affected by P-CO2 and organic ligands at 25 degrees C, 1998, Lebron I. , Suarez D. L. ,
This study was conducted to develop a model for the precipitation rate of calcite under varying CO2 partial pressures and concentrations of dissolved organic carbon (DOG). Precipitation rates of calcite were measured in solutions with supersaturation values (Omega) between 1 and 20 and in the presence of 2 m(2)L(-1) of calcite. Experiments were run at partial pressures of CO2 (P-CO2) in the range of 0.035-10 kPa and DOC concentrations in the range of 0.02-3.50 mM. The effects of these two variables were quantified separately for the precipitation mechanisms of crystal growth and heterogeneous nucleation. We found an increase in precipitation rate (at constant Omega) when P-CO2 increased. For constant Omega, we also found a linear relationship between calcite precipitation rate and activity of CaHCO3, indicating that CaHCO3 species have an active role in the mechanism of calcite precipitation. These findings suggest that the increase in the precipitation rate with higher P-CO2 levels is likely caused by the increase in the negative charge on the calcite surface together with an increase in the activity of CaHCO3 species in solution. The mechanism of inhibition of calcite crystal growth by organic ligands has been shown to be surface coating of the crystals by DOG. The amount of DOC adsorbed on the surface of the calcite crystals follows a Langmuir isotherm for all the P-CO2 levels studied; however, the amount of DOC necessary to inhibit calcite precipitation increased. With increasing P-CO2, the negative charge on the crystal increases, which affects crystal growth, but also these increases in P-CO2 cause a decrease in the solution pH and increase in the ionic strength for constant Omega. Solution pH and ionic strength affect the structure and degree of dissociation of the organic functional groups, which in turn affects the and DOC concentration on the inhibition of crystal growth and heterogeneous nucleation. The effect of P-CO2 and DOC concentration on the precipitation rate of calcite is expressed in a precipitation rate model which reflects the contributions of crystal growth and heterogeneous nucleation. Copyright (C) 1998 Elsevier Science Ltd

The inhibiting action of intrinsic impurities in natural calcium carbonate minerals to their dissolution kinetics in aqueous H2O-CO2 solutions, 1999, Eisenlohr L, Meteva K, Gabrovsek F, Dreybrodt W,
We have measured the surface controlled dissolution rates of natural calcium carbonate minerals (limestone and marble) in H2O-CO2 solutions by using free drift batch experiments under closed system conditions with respect to CO2, at 10 degrees C with an initial partial pressure of carbon dioxide of 5.10(-2) atm. All experiments revealed reaction rates F, which can be described by the empirical relation: F-n1 = k(n1) . (1 - c/c(eq))(n1) for c < c(s), which switches to a higher order n(2) for calcium concentrations c greater than or equal to c(s) described by F-n2 = k(n2) . (1 - c/c(eq))(n2) . k(n1) and k(n2) are rate constants in mmole/(cm(2) . s), c(eq) is the equilibrium concentration with respect to calcite. The values of the constants n(1), n(2), k(n1), k(n2) and c(s) depend on the V/A ratio employed, where V is the volume of the solution and A is the surface area of the reacting mineral. Different calcium carbonate minerals exhibit different values of the kinetic constants. But generally with increasing V/A, there is a steep variation in the values of all kinetic constants, such that the rates are reduced with increasing V/A ratio. Finally with sufficiently large V/A these values become constant. These results are explained by assuming intrinsic inhibitors in the bulk of the mineral. During dissolution these are released from the calcite matrix and are adsorbed irreversibly at the reacting surface, where they act as inhibitors. The thickness d of the mineral layer removed by dissolution is proportional to the VIA ratio. The amount of inhibitors released per surface area is given by d c(int), where c(int) is their concentration id the bulk of the mineral. At low thicknesses up to approximate to 3 . 10(-4) cm in the investigated materials, the surface concentration of inhibitors increases until saturation is attained for thicknesses above this value. To analyze the surface concentration and the type of the inhibitors we have used Auger spectroscopy, which revealed the presence of aluminosilicate complexes at the surface of limestone, when a thickness of d approximate to 10(-3) cm had been removed by dissolution. In unreacted samples similar signals, weaker by one order of magnitude, were observed. Depth profiles of the reacted sample obtained by Ar-ion sputtering showed the concentration of these complexes to decrease to the concentration observed in the unreacted sample within a depth of about 10 nm. No change of the concentration with depth was observed in unreacted samples. These data suggest that complexes of aluminosilicates act as inhibitors, although other impurities cannot be excluded. Copyright (C) 1999 Elsevier Science Ltd

Karst aquifer evolution in fractured, porous rocks, 2000, Kaufmann G. , Braun J. ,
The evolution of flow in a fractured, porous karst aquifer is studied by means of the finite element method on a two-dimensional mesh of irregularly spaced nodal points. Flow within the karst aquifer is driven by surface recharge from the entire region, simulating a precipitation pattern, and is directed toward an entrenched river as a base level. During the early phase of karstification both the permeable rock matrix, modeled as triangular elements, and fractures within the rock matrix, modeled as linear elements, carry the now. As the fractures are enlarged with time by chemical dissolution within the system calcite-carbon dioxide-water, flow becomes more confined to the fractures. This selective enlargement of fractures increases the fracture conductivity by several orders of magnitude during the early phase of karstification. Thus flow characteristics change from more homogeneous, pore-controlled flow to strongly heterogeneous, fracture-controlled flow. We study several scenarios for pure limestone aquifers, mixed sandstone-limestone aquifers, and various surface recharge conditions as well as the effect of faulting on the aquifer evolution. Our results are sensitive to initial fracture width, faulting of the region, and recharge rate

Dam sites in soluble rocks: a model of increasing leakage by dissolutional widening of fractures beneath a dam, 2003, Romanov D. , Gabrovsek F. , Dreybrodt W. ,
Water flowing through narrow fissures and fractures in soluble rock, e.g. limestone and gypsum, widens these by chemical dissolution. This process, called karstification, sculptures subterranean river systems which drain most of their catchment. Close to dam sites, unnaturally high hydraulic gradients are present to drive the water impounded in the reservoir downstream through fractures reaching below the dam. Under such conditions, the natural process of karstification is accelerated to such an extent that high leakage rates may arise, which endanger the operation of the hydraulic structure. Model simulations of karstification below dams by coupling equations of dissolutional widening to hydrodynamic flow are presented. The model scenario is a dam 100 in wide in limestone or gypsum. The modelling domain is a two-dimensional slice 1 m wide directed perpendicular to the dam. It extends 375 in vertically and 750 in horizontally. The dam is located in its center. This domain is divided by fractures and fissures into blocks of 7.5 x 7.5 x 1 m. The average aperture width of the fractures is 0.02 cm. We performed model runs on standard scenarios for a dam site in limestone with the height H of impounded water 150 in, a horizontal impermeable apron of width W=262 m and a grouting curtain reaching down to a depth of G=97 m. In a second scenario, we changed these construction features to G=187 m and W=82 m. To calculate widening of the fractures, well-established experimental data on the dissolution of limestone and gypsum have been used as they occur in such geochemical settings. All model runs show similar characteristic behaviour. Shortly after filling, the reservoir exhibits a small leakage of about 0.01 m(-3) s(-1), which increases steadily until a breakthrough event occurs after several decades with an abrupt increase of leakage to about 1 m(3) s(-1) within the short time of a few years. Then, flow in the fractures becomes turbulent and the leakage increases to 10 m(3) s(-1) in a further time span of about 10 years. The widths of the fractures are visualized in various time steps. Small channels propagate downstream and leakage rises slowly until the first channel reaches the surface downstream. Then breakthrough occurs, the laminar flow changes to turbulent and a dense net of fractures which carry flow is established. We performed a sensitivity analysis on the dependence of breakthrough times on various parameters, determining breakthrough. These are the height of impounded water H, the depth G of grouting, the average aperture width a(0) of the fractures and the chemical parameters, which are c(eq) the equilibrium concentration of Ca with respect to calcite and the Ca-concentration c(in) of the inflowing water. The results show that the most critical parameter is a(0). At fracture aperture widths of 0.01 cm, breakthrough times are above 500 years. For values of a(0)>0.02 cm, however, breakthrough times are within the lifetime of the structure. We have also modelled dam sites in gypsum, which exhibit similar breakthrough times. However, after breakthrough, owing to the much larger dissolution rates of gypsum, the time until unbearable leakage is obtained, is only a few years. The modelling can be applied to complex geological settings, as phreatic cave conduits below the dam, or a complex stratigraphy with varying properties of the rock with respect to hydraulic conductivity and solubility. A few examples are given. In conclusion, our results support the assumption that increasing leakage of dam sites may be caused by dissolutional widening of fractures. (C) 2003 Elsevier Science B.V. All rights reserved

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