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.

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.

Carbonate aquifers are some of most challenging to characterize because dissolution can greatly enhance permeability, but its effects are often difficult to determine. This study analyzes data from caves, wells, and tracer tests to explore the extent of solution channel networks and the factors that influence their development. The nonlinear dissolution kinetics of calcite, mixing of waters with different CO2 concentrations, and unstable dissolution fronts all promote the development of solution channels, which are widespread in unconfined carbonate aquifers. Fractures are important for guiding channels at a local scale, but hydraulic gradients are the dominant control at a regional scale. Channels provide continuous, large-aperture pathways that result in rapid groundwater flow. Small channels are much more abundant than large channels, and often account for most of the permeability measured in wells. Caves represent the largest channels; they are more common in limestone than in dolostone, and the development of caves rather than smaller channels is also favored where there is sparse fracturing, low matrix porosity, and the presence of sinking stream recharge rather than percolation recharge. Solution channel networks have fractal properties, and their presence explains why carbonate aquifers have higher permeability than aquifers in any other rock type.

Carbonate aquifers are some of most challenging to characterize because dissolution can greatly enhance permeability, but itseffects are often diffi cult to determine. This study analyzes data from caves, wells, and tracer tests to explore the extent of solution channel networks and the factors that infl uence their development. The nonlinear dissolution kinetics of calcite, mixing of waters with different CO2 concentrations, and unstable dissolution fronts all promote the development of solution channels, which are widespread in unconfi ned carbonate aquifers. Fractures are important for guiding channels at a local scale, but hydraulic gradients are the dominant control at a regional scale. Channels provide continuous, large-aperture pathways that result in rapid groundwater fl ow. Small channels are much more abundant than large channels, and often account for most of the permeability measured in wells. Caves represent the largest channels; they are more common in limestone than in dolostone, and the development of caves rather than smaller channels is also favored where there is sparse fracturing, low matrix porosity, and the presence of sinking stream recharge rather than percolation recharge. Solution channel networks have fractal properties, and their presence explains why carbonate aquifers have higher permeability than aquifers in any other rock type

The processes of initiation and development of characteris­tic surface karst landforms and underground caves are nearly all chemical processes. This paper reviews the advances in understanding of karst chemistry over the past 60 years. The equilibrium chemistry of carbonate and sulfate dissolution and deposition is well established with accurate values for the necessary constants. The equations for bulk kinetics are known well enough for accurate modeling of speleogenetic processes but much is being learned about atomic scale mechanisms. The chemistry of karst waters, expressed as parameters such as total dissolved carbonates, saturation index, and equilibrium carbon dioxide pressure are useful tools for probing the internal char­acteristics of karst aquifers. Continuous records of chemical parameters (chemographs) taken from springs and other karst waters mapped onto discharge hydrographs reveal details of the internal flow system. The chemistry of speleothem deposi­tion is well understood at the level of bulk processes but much has been learned of the surface chemistry on an atomic scale by use of the atomic force microscope. Least well understood is the chemistry of hypogenetic karst. The main chemical reac­tions are known but equilibrium modeling could be improved and reaction kinetics are largely unknown.