Dissolution kinetics of calcium carbonate in seawater. Theory of calcite solution, 1974, Berner R. A. , Morse J. W.

The role of solution kinetics in the development of karst aquifers, 1977, White W. B.

Critical review of the kinetics of calcite dissolution and precipitation, 1979, Plummer L. N. , Parkhurst D. C. , Wigley T. M. L.

Mixing corrosion in CaCO3/1bCO2/1bH2O systems and its role in the karstification of limestone areas, 1981, Dreybrodt W,

Mixtures of two saturated H2O/1bCO2/1bCaCO3 solutions of different chemical composition gain renewed capability of dissolving calcite. This is an important mechanism in the solution processes of limestone during karstification. Using recent data on the kinetics of calcite dissolution, dissolution rates in mixture corrosion are calculated. In the region of the chemical composition of natural karst waters the solution rate is approximated by:R=-[alpha]([Ca2] - [Ca2]s where [Ca2], [Ca2]s are the concentrations of the Ca2 ion in the solution and at saturation, respectively. [alpha] ranges from 10-4 to 3[middle dot]10-4 cm s-1.This result is applied to the solution of limestone in karst water mixtures flowing in cylindrical conduits. The saturation length, i.e. the length xs which the solution has to travel to drop to 37% of its renewed dissolving capability, is calculated in the region of turbulent flow. This region starts at conduit radii R of several millimeters. At the onset of turbulent flow the saturation length is 260 m, increasing with R1.665. The increase of conduit radii is calculated from the dissolution rates of calcite solution to be on the order of 10-3 cm yr.-1.The results are discussed for a comprehensive model of karstification and cave development, which for the first time gives a realistic theoretical time region for cave development, in agreement to experience

The kinetics of dissolution of dolomite in CO2?H20 systems at 1.5° to 65° N and 0 to 1 atm PC02, 1982, Busenberg E. , Plummer L. N.

A possible mechanism for growth of calcite speleothems without participation of biogenic carbon dioxide, 1982, Dreybrodt W,

Using Plummer et al.'s [11] rate equations on the dissolution and deposition of CaCO3 in H2O---CO2 systems, we have calculated deposition rates of CaCO3 to stalagmites in caves which are covered by glaciers or bare karst. In this case no biogenic CO2 from vegetated soil is available and the deposition of CaCO3 involves only atmospheric CO2. The mechanism of deposition proceeds by a temperature effect. Cold melting waters of about 0[deg]C dissolve CaCO3 under open system conditions at the surface of the rock. When this solution saturated with respect to CaCO3, flows through the limestone rock its temperature increases by several degrees. Therefore, it becomes supersaturated, and CaCO3 is deposited under open system conditions in the warmer cave. Maximal growth rates of about 10-3 cm/year are possible. From the kinetics of the deposition of CaCO3 from the thin water films present at the surface of stalagmites we are able to estimate the isotopic composition of carbon in the CaCO3 deposited on the stalagmites to be approximately [delta]13C = %, which is close to some observed values.From our data we conclude that substantial growth of stalagmites is possible during glacial periods as well as in areas of bare karst, a question which was not resolved up to now

Rate processes: chemical kinetics and karst landform development,, 1984, White W. B.

THE KINETICS OF CALCITE DISSOLUTION AND PRECIPITATION IN GEOLOGICALLY RELEVANT SITUATIONS OF KARST AREAS .1. OPEN SYSTEM, 1985, Buhmann D, Dreybrodt W,

Dissolution kinetics of dolomite: effects of lithology and fluid flow velocity., 1985, Herman J. S. , White W. B.

A comparative study of the dissolution kinetics of calcite and aragonite, 1986, Busenberg E. , Plummer L. N.

Kinetics of Calcite Dissolution and its Consequences to Karst Evolution from the Initial to the Mature State, 1987, Drybrodt, Wolfgang

Comparative study of the kinetics and mechanisms of dissolution of carbonate minerals, 1989, Chou L. , Garrels R. M. , Wollast R.

Groundwater chemistry and cation budgets of tropical karst outcrops, Peninsular Malaysia, I. Calcium and magnesium, 1989, Crowther J,

The discharge and chemical properties of 217 autogenic groundwaters were monitored over a 1-yr period in the tower karsts of central Selangor and the Kinta Valley, and in the Setul Boundary Range. Because of differences in soil PCO2, calcium concentrations are significantly higher in the Boundary Range (mean, 82.5 mg l-1) than in the tower karst terrain (44.6 mg l-1). Local differences in both source area PCO2 and amounts of secondary deposition underground cause marked intersite variability, particularly in the tower karst. Dilution occurs during flood peaks in certain conduit and cave stream waters. Generally, however, calcium correlates positively with discharge, since the amount of secondary deposition per unit volume of water decreases at higher flows. Magnesium concentrations and Mg:Ca Mg ratios of groundwaters are strongly influenced by bedrock composition, though bedrock heterogeneity and the kinetics and equilibria of carbonate dissolution reactions preclude extremely low or high Mg:Ca Mg values. Net chemical denudation rates range from 56.6 to 70.9 m3km2yr-1.The results are considered in relation to cation fluxes in surface runoff, soil throughflow and nutrient cycling. Preliminary calcium and magnesium budgets show that (1) dissolutional activity is largely confined to the near-surface zone; and (2) the annual uptake of calcium and magnesium by tropical limestone forests is similar in magnitude to the net solute output in groundwaters

THE ROLE OF DISSOLUTION KINETICS IN THE DEVELOPMENT OF KARST AQUIFERS IN LIMESTONE - A MODEL SIMULATION OF KARST EVOLUTION, 1990, 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