Kinetics and mechanisms of cyanobacterially induced precipitation of magnesium silicate

Abstract

The biomineralization of CO₂, in the form of carbonate minerals, is considered as one of the efficient solutions of atmospheric CO₂ removal, allowing stable and sustainable storage of this greenhouse gas. Cyanobacteria are among the most powerful microorganisms capable of precipitating carbonate minerals, both in the present and in the past. In the modern environments, high Si concentration during geoengineering biomineralization could occur due to dissolution of Mg-bearing primary silicates such as olivine. However, most of experimental studies aimed to understand the formation of these carbonates were performed in Si-poor solutions. Thus, experimental characterizations of the nature, rate, and stoichiometry of precipitated minerals in Si-rich solutions in the presence of bacteria are lacking. The present study attempted to reproduce, in controlled laboratory experiments, the processes of biomineralization in a carbonate- and Mg-bearing medium having high Si concentrations (2–4 mM, which is below the saturation with respect to amorphous silica). These experiments have been carried out in the presence of three contrasting cyanobacteria: Synechococcus sp., Chroococcidiopsis sp. and Aphanothece clathrata in order to characterize the rate of formation, stoichiometry and mineralogical nature of precipitates. The results demonstrated significant role of cyanobacteria in the precipitation of carbonate and silicate minerals by increasing the pH of the medium during photosynthesis. Magnesium precipitation rates measured between 50 and 150 h of reaction time ranged from 0.05 to 0.5 mmol h⁻¹ g_dry¹ and decreased (Synechococcus sp. and Chroococcidiopsis sp.) or increased (A. clathrata) with an increase in the Si:Mg ratio in solution. The abiotic instantaneous rates of Mg and Si removal from alkaline solutions were similar to those in the presence of cyanobacteria at the same pH value suggesting that photosynthetically induced pH rise was the main factor of mineral formation. The transmission electron microscopy (TEM) and spectroscopic observations and associated analyses identified an amorphous magnesium silicate together with hydrous Mg carbonates (hydromagnesite). The formation of carbonate solid phase at high Mg: Si ratios indicated the potential for the removal of inorganic carbon at pH > 10. The difference in the degree of C removal between different species was primarily linked to different degree of pH rise during photosynthesis. Taken together, the results obtained in this study allowed an efficient reproduction of combined magnesium hydroxo-carbonates and hydrous silicates precipitation under cyanobacterial activity, suitable for geoengineering of biologically controlled CO₂ sequestration in Si-Mg-carbonate-bearing solutions.