Dissolution-filling mechanism of atmospheric precipitation controlled by both thermodynamics and kinetics

Affected by structural uplift, the Ordovician carbonate rockbed in the Tarim Basin, China, was exposed to dissolution and reformation of atmospheric precipitation many times, and formed a large quantity of karst caves serving as hydrocarbon reservoir. However, drilling in Tahe area showed that many large karst caves, small pores and fractures are filled by calcite, resulting in decrease in their reservoir ability. Calcite filled in the karst caves has very light oxygen isotopic composition and Sr-87/Sr-86 ratio. Its delta O-18(PDB) ranges from -21.2aEuro degrees to 13.3aEuro degrees with the average of -16.3aEuro degrees and its Sr-87/Sr-86 ratio ranges from 0.709561 to 0.710070 with the average of 0.709843. The isotope composition showed that calcite is related to atmospheric precipitation. Theoretic analyses indicated that the dissolving and filling actions of the precipitation on carbonate rocks are controlled by both thermodynamic and kinetic mechanisms. Among them, the thermodynamic factor determines that the precipitation during its flow from the earth surface downward plays important roles on carbonate rocks from dissolution to saturation, further sedimentation, and finally filling. In other words, the depth of the karstification development is not unrestricted, but limited by the precipitation beneath the earth surface. On the other hand, the kinetic factor controls the intensity, depth, and breadth of the karstification development, that is, the karstification is also affected by topographic, geomorphologic, climatic factors, the degree of fracture or fault, etc. Therefore, subject to their joint effects, the karstification of the precipitation on the Ordovician carbonate rocks occurs only within a certain depth (most about 200 m) under the unconformity surface, deeper than which carbonate minerals begin to sedimentate and fill the karst caves that were formed previously.