Thermodynamic equilibrium, kinetics, activation barriers, and reaction mechanisms for chemical reactions in Karst Terrains

Chemical reactions pertinent to karst systems divide broadly into (a) speciation reactions within aqueous solutions, (b) dissolution/precipitation and other acid/base reactions between aqueous solutions and solid minerals, and (c) redox reactions involving various carbon and sulfur-bearing species. As a backdrop against which other chemistry can be evaluated, selected phase diagrams and equilibrium speciation diagrams were calculated for the system CaUMgUOUHUCUS. The kinetics of reactions within this system span time scales from milliseconds for homogeneous reactions in solution through hundreds of hours for carbonate mineral dissolution reactions, to geologic time scales for reactions such as the aragonite/calcite inversion or the oxidation/reduction of native sulfur. In purely inorganic systems, kinetic barriers, typically on the order of tens of kJ/mole, are set by nucleation processes and by activated complex formation. Biological processes impact the purely inorganic chemistry by the following mechanisms: (a) Secretions and waste products from biological activity or consumption of CO2 by organisms changes the chemistry in the microenvironments of reaction surfaces. Oxidation potentials, pH, and ion activities may be modified, thus shifting equilibria. (b) Reaction rates may be increased due to modification of activated complexes and thus the activation barriers to reaction. (c) Organic compounds or microorganisms may act as substrates, thus lowering nucleation barriers. The preservation of microorganisms in cave deposits does not necessarily prove a cause and effect relationship.