Two different cyanobacterial biofilms from German karstwater creeks were investigated with respect to their photosynthetic effect on Ca 2C removal and potential CaCO 3 precipitation in artificial creek waters of different CO 2 partial pressures at a given, constant calcite supersaturation. CO 2 partial pressures were adjusted to 350 ppmV, 2200 ppmV and 8700 ppmV respectively, covering the range of Phanerozoic atmospheric CO 2 partial pressures inferred from palaeosoils, stomatal indices and model calculations. Microsensor measurements of calcium, pH and oxygen revealed differences in the potential to precipitate CaCO 3 between the two model organisms Tychonema-relative strain SAG 2388 and Synechococcus sp. strain SAG 2387. Whereas a strong removal of Ca 2C from the solution was measured at Tychonema-relative biofilm, the Synechococcus sp. biofilm exercised a much lower Ca 2C removal during photosynthesis. Photosynthesis was enhanced in both organisms with increasing CO 2 and HCO 3 ¡ , as indicated by enhanced O 2 production, but only for the motile filamentous taxon Tychonema-relative a concomitantly increasing calcium removal was measured. However, model calculations indicate that this short-term Ca 2C binding in the Tychonema-relative is due to complexation to exopolymers or oscillin, with no immediate CaCO 3 precipitation. In contrast, Ca 2C and pH measurements at Synechococcus sp. biofilm could be consistent with immediate CaCO 3 precipitation at the cells. In both biofilms, pH gradients increase with increasing pCO 2 from 350 to 2200 ppmV due to enhanced photosynthesis, but decrease at a pCO 2 of 8700 ppmV despite of further enhanced photosynthesis. This observation, regardless whether CO 2 or HCO 3 ¡ is used by the cyanobacteria, is in accordance with hydrochemical modeling demonstrating an increased DIC buffering at high pCO 2 conditions. These results indicate that the potential of cyanobacteria to form spatially defined calcification pattern via pH gradients at their cell envelopes ('calcified cyanobacteria') increases at elevated pCO 2 , while at high pCO 2 conditions Ca 2C binding and lowered pH microgradients lead to spatially diffuse calcification without defined cell envelope precipitates.