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Featured articles from Cave & Karst Science Journals

Characterization of minothems at Libiola (NW Italy): morphological, mineralogical, and geochemical study, Carbone Cristina; Dinelli Enrico; De Waele Jo

Chemistry and Karst, White, William B.

The karst paradigm: changes, trends and perspectives, Klimchouk, Alexander

Long-term erosion rate measurements in gypsum caves of Sorbas (SE Spain) by the Micro-Erosion Meter method, Sanna, Laura; De Waele, Jo; Calaforra, José Maria; Forti, Paolo

The use of damaged speleothems and in situ fault displacement monitoring to characterise active tectonic structures: an example from Zapadni Cave, Czech Republic , Briestensky, Milos; Stemberk, Josef; Rowberry, Matt D.;

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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**system h2o-co2-caco3**(Keyword) returned**5**results for the whole karstbase: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

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

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

During the chemically based recession flow phase of karstic springs the carbonate (dissolved limestone) concentration can be expressed as negative power of the flow rate. The empirically determined Conc/Q relationship allows two parameters (alpha and A) to be defined, of which one (alpha) depends on the geometric dimensions of the saturated (submerged) karstic network. In this paper we present a deterministic model which simulates the concentration of carbonate at the outlet of a network of circular rectilinear conduits as a function of flow rate. This model, based on hydraulic principles and the calcite dissolution kinetics, allows the sensitivity of the alpha and A parameters to be studied under different chemical, physical and geometric scenarios. Simulation results show that A is a function of the calcite saturation concentration, whereas alpha depends on the spatial dimensions of the karstic network (void length and aperture). The deterministic model results were applied to real karstic systems to evaluate the geometric dimensions of submerged karstic networks. (C) 2002 Elsevier Science B.V. All rights reserved

The early evolution of karst aquifers depends on a manifold of initial and boundary conditions such as geological setting, hydrologic properties of the initial aquifer, and petrologic properties of the rock. When all water entering at various inputs into the aquifer has equal chemical composition with respect to the system H2O-CO2-CaCO3 early evolution under conditions of constant head exhibits breakthrough (BT) behaviour. If the chemical compositions of the input waters are different, deep in the aquifer where the saturated solutions mix renewed aggressiveness occurs, and additional dissolutional widening of fractures by mixing corrosion (MC) changes the hydrologic properties of the aquifer. To study the impact of MC on the evolution of karst we have modelled a simple karst aquifer consisting of a confined limestone bed, with two symmetrically located inputs at constant head and open flow conditions along the entire width at base level. To calculate dissolutional widening of the fractures the well-known dissolution kinetics of limestone was used, which is linear up to 90% of saturation with respect to calcite and then switches to a nonlinear fourth order rate law. First, two extremes are modelled: (a) Both inputs receive aggressive water of equal chemical composition with [Ca2] = 0.75[Ca2](eq). In this case two channels migrate downstream with that from one input more competitive and reaching base level first, causing BT. (b) Water at both inputs is saturated with respect to calcite, but in equilibrium with different partial pressures Of CO2. Therefore, dissolution widening can occur only where these waters mix. A central channel starts to grow extending down-head until base level is reached. Flow rates through the aquifer first rise and become constant after the channel has reached base level. In the following runs these two extreme modes of karstification are combined. The waters entering have different chemical compositions and therefore different equilibrium concentrations [Ca2](eq). This allows MC to be active. They are also undersaturated with the inflowing solutions at concentration [Ca2](in) = f[Ca2](eq) where f is the ratio of saturation. In comparison to the extreme limit (a) the action of MC now creates permeability where the solutions mix and diverts the evolution of conduits into this region. Finally one conduit reaches base level and causes BT. This behaviour is found for f = 0.7, 0.9, and 0.96. For solutions more close to equilibrium with respect to calcite (f = 0.99, 0.9925, and 0.995) BT behaviour is replaced by a steady increase in flow rates. In the early state as in the case of MC controlled evolution (case b) a central channel not connected to the input is created by MC and reaches base level. After this event, further increase in flow rates is caused by slow dissolutional widening by the slightly undersaturated input solutions flowing towards the central channel. Comparison of the various model aquifers at termination of the computer runs reveals significant differences in their properties caused solely by changes of the hydrochemical boundary conditions. (C) 2003 Elsevier Science B.V. All rights reserved

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