The enigma that caves and other solution openings form in carbonate rocks at great depths below land surface rather than forming from the surface downward can be explained by the generation of CO2 within the aquifer system. In the proposed model, CO2 is generated by the oxidation of particulate and/or dissolved organic carbon that is transported from the land surface deep into the unsaturated zone by recharging ground water. The organic material is oxidized to CO2 by aerobic bacteria utilizing oxygen that diffuses in from the atmosphere. Because gas transport in the unsaturated zone is controlled largely by diffusion, steady-state generation of even minute amounts of CO2 deep in the unsaturated zone results in the creation of large concentrations of CO2 at depth as it establishes a concentration gradient to the surface or other sink. Ground water descending into these areas of high CO2 concentration becomes thermodynamically subsaturated with respect to carbonate minerals and is able to dissolve them, thus forming the observed solution opening at depth.