KarstBase a bibliography database in karst and cave science.

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.

Engineering challenges in Karst, Stevanović, Zoran; Milanović, Petar

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

Featured articles from other Geoscience Journals

Geochemical and mineralogical fingerprints to distinguish the exploited ferruginous mineralisations of Grotta della Monaca (Calabria, Italy), Dimuccio, L.A.; Rodrigues, N.; Larocca, F.; Pratas, J.; Amado, A.M.; Batista de Carvalho, L.A.

Karst processes and landforms, De Waele, J.

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

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**dissolution kinetics**(Keyword) returned**54**results for the whole karstbase: Showing

**1**to**15**of 54Limestone 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

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

Karstification is a slow geodynamical process, controlled by the interaction between dissolution kinetics and flow dynamics. Moreover, mechanisms of network clogging by calcite precipitation or non-soluble clay accumulation are slow and continuous phenomena. This evolution of a karst system can be widely modified during exceptional rainfall episodes, such as the 22/09/92 storm (> 300 mm) near Vaison-la-Romaine. Such an impulse can modify the hydraulical behaviour of a massif, by unclogging the outlets of the saturated zone or the drainage network of the aquifer, and change hydrodynamical features of a spring (storage capacity etc.). This phenomenon has been demonstrated in a north Vaucluse karst aquifer whose recession coefficient has increased 7-fold and stored volume divided by 6

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

Experiments with gypsum in aqueous solutions at 25 degrees C, low ionic strengths, and a range of saturation states indicate a mixed surface reaction and diffusional transport control of gypsum dissolution kinetics. Dissolution rates were determined in a mixed flow/rotating disc reactor operating under steady-state conditions, in which polished gypsum discs were rotated at constant speed and reactant solutions were continuously fed into the reactor. Rates increase with velocity of spin under laminar conditions (low rates of spin), but increase asymptotically to a constant rate as turbulent conditions develop with increasing spin velocity, experiencing a small jump in magnitude across the laminar-turbulent transition. A Linear dependence of rates on the square root of spin velocity in the laminar regime is consistent with rates being limited by transport through a hydrodynamic boundary layer. The increase in rate with onset of turbulence accompanies a near discontinuous drop in hydrodynamic boundary layer thickness across the transition. A relative independence of rates on spinning velocity in the turbulent regime plus a nonlinear dependence of rates on saturation state are factors consistent with surface reaction control. Together these behaviors implicate a 'mixed' transport and reaction control of gypsum dissolution kinetics. A rate law which combines both kinetic mechanisms and can reproduce experimental results under laminar flow conditions is proposed as follows: R = k(t) {1 - Omega(b)() zeta [1 - (1 2(1 - Omega(b)())(1/2)]} where k(t) is the rate coefficient for transport control, and Omega(b)() is the mean ionic saturation state of the bulk fluid. The dimensionless parameter zeta(=Dm(eq)()/2 delta k() where m(eq)() = mean ionic molal equilibrium concentration, D is the diffusion coefficient through the hydrodynamic boundary layer, delta equals the boundary layer thickness and k() is the rate constant for surface reaction control) indicates which process, transport or surface reaction, dominates, and is sensitive to the hydrodynamic conditions in the reactor. For the range of conditions used in our experiments, zeta varies from about 1.4 to 4.5. Rates of gypsum dissolution were also determined in situ in a cavern system in the Permian Blaine Formation, southwestern Oklahoma. Although the flow conditions in the caverns were not determinable, there is good agreement between lab- and field-determined rates in that field rate magnitudes lie within a range of rates determined experimentally under zero to low spin velocities A numerical model coupling fluid flow and gypsum reaction in an idealized circular conduit is used to estimate the distance which undersaturated solutions will travel into small incipient conduits before saturation is achieved. Simulations of conduit wall dissolution showed-member behaviors of conduit formation and surface denudation that depend on flow boundary conditions (constant discharge or constant hydraulic gradient and initial conduit radius. Surface-control of dissolution rates. which becomes more influential with higher fluid flow velocity, has the effect that rate decrease more slowly as saturation is approached than otherwise would occur if rates were controlled by transport alone. This has the effect that reactive solutions can penetrate much farther into gypsum-bearing karst conduits than heretofore thought possible, influencing timing and mechanism of karst development as well as stability of engineered structures above karst terrain

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

The relative dissolution kinetics of the Lirio Limestone and the Isla de Mona Dolomite were determined by dissolving discs of various samples in CO2 -saturated solutions. Rate curves for carbonate dissolution were determined by monitoring pH and specific conductance as a function of time. Dissolution rates for limestone samples were distinctly higher than rates for dolomite samples but the rate curves had similar shapes. Initial rates for limestones averaged 12.53 mmol m-2 sec-1 compared with 8.53 for dolomite. The limestone rates are comparable with those measured on single crystal calcite but the dolomite rates are higher than rates measured on Paleozoic dolomites. The relative dissolution rates are sufficient to be a factor in explaining the concentration of caves at the limestone/dolomite contact but may not be the only controlling factor

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

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