Quantifying the link between cyanobacterial activity and the carbon isotope signature of precipitated carbonate minerals is crucial for reconstructing the environmental conditions present at the time of carbonate mineral formation. In this study, calcite was precipitated in the presence and absence of Synechococcus sp. cyanobacteria in batch reactors. The temporal evolution of the carbon isotope composition of calcite ( 13 CCalcite) and dissolved inorganic carbon ( 13 CDIC) was monitored to evaluate the rate and degree to which the carbon isotope compositions in calcite are modified during and after its precipitation. The presence of cyanobacteria promoted calcium carbonate formation by increasing fluid pH and the CaCO3 saturation state. It also changed significantly the carbon isotope composition of dissolved inorganic carbon due to the preferential incorporation of 12 C into the biomass. This generated an isotope disequilibrium between the calcite and the aqueous fluid phase over time after the calcite precipitated. The carbon isotope composition of the calcite evolved continuously towards mineral-fluid isotope equilibrium after its precipitation, at geometric surface area normalized rates ranging from 1.75×10 -14 to 1.71×10 -13 mol 13 C/m 2 /s. These rates are sufficiently fast such that the 13 CDIC value of aqueous fluids in calcite-rich rocks would be buffered by the 13 CCalcite value of the co-existing calcite. Mass balance calculations suggest that the carbon isotope composition of calcite could change noticeably when the calcite is in isotope disequilibrium with its co-existing fluid, for example through the presence of a local 12 C sink such as photosynthetic microorganisms or 12 C source such as decomposition of organic material.
KeywordsCarbon isotopes, calcite, cyanobacteria, isotope re-equilibration 13 ) as summarized in Fig. 1. The δ C DIC 13values in these experiments are initially controlled by the carbon isotope composition of the carbonate and bicarbonate powder added to water to produce the initial reactive fluids. This value is subsequently influenced by 1) carbon exchange with the atmospheric CO 2 that was continuously bubbled in the reactors, 2) photosynthetic uptake of DIC by growing cyanobacteria, 3) live cell respiration and dead cell lysis together with the subsequent heterotrophic degradation of organic compounds to dissolved carbon species, and 4) DIC removal from the fluid by calcite precipitation. These processes are described in detail in the following section.
Equilibrium fractionation between atmosphericCO2 and DIC An estimate of δ C DIC 13 values in equilibrium with the atmosphere can be made by taking account of the distinct equilibrium fractionation factors of each major carbon species present in the aqueous fluids using (Myrttinen et al., 2012): δ 13 C DIC = ∑ (𝑥 𝑖 • (δ 13 C CO 2 + 10 3 ln α 13 C 𝑖−CO 2(g) )) 𝑖 ,where 𝑥 𝑖 designates the mole fraction of the ith aqueous carbon species and δ 13 C CO 2 designates the carbon isotope composition of atmospheric CO 2 , which wa...