Biomimetic Mineralization of Ca-Mg Carbonates: Relevance to Microbial Cells and Extracellular Polymeric Substances.

Research on Ca-Mg carbonate crystallization and phase transition regulated by microbial cells and extracellular polymeric substances (EPS) is significant for carbon sequestration, remediation of polluted soil and water, and synthesis of functional biomaterials. This study focused on the mineralogical transformation from amorphism to crystal, and interaction among cells, EPS, and minerals. By tracing the law of mineral growth and morphological evolution, the influences of cells and EPS on mineral formation were investigated. The results revealed that calcification and the template of rod-shaped cells of strain HJ-1 were the basis for the formation of dumbbell-shaped particles, and directional aggregation and differential growth were the keys to the development and stability of dumbbells. Cell participation had a noticeable impact on mineral prototypes, instead of determining the polymorphism. EPS contributed to aragonite formation and stability. The acidic amino acids or proteins in EPS were likely to cause an increase in MgCO3 content in Mg-calcite. EPS promoted aggregation of particles and induced spherical formation. Exopolysaccharides and proteins were the main components of EPS that can affect carbonate mineralization. EPS could influence the morphology and polymorphism by providing nucleation sites, interacting with Mg2+, adsorbing or incorporating mineral lattices, and inducing particle aggregation.

Comparison of carbonate precipitation induced by Curvibacter sp. HJ-1 and Arthrobacter sp. MF-2: Further insight into the biomineralization process.

Microorganisms are generally involved in the nucleation, growth and phase transformation of carbonate minerals, and influence the development of their morphology and polymorphism. However, understanding of the process of microbially induced carbonate precipitation (MICP) remains limited. Herein, MICP experiments were carried out using Curvibacter sp. HJ-1 and Arthrobacter sp. MF-2 in M2 medium, and the processes of MICP were monitored. Bacterial cells induced the precipitation of carbonate by creating favorable physicochemical conditions and acting as nucleation templates for carbonate particles and thereby, markedly influenced the morphology and growth of the carbonate structure. The extracellular polymeric substance (EPS) secreted by the bacteria was readily absorbed by the precipitated carbonate, which modified its crystal growth orientation. The MgCO3 content of Mg-calcite, induced by MF-2, was dramatically higher than that induced by HJ-1; HJ-1 promoted the formation and stability of aragonite. Multiple formation mechanisms coexisted during the evolution process of the mineral morphologies in the presence of the bacteria. The spherulites observed mainly evolved from dumbbell-like precursors in the presence of MF-2, whereas aggregate growth was the main formation mechanism of radial spherulites in the presence of HJ-1.

Bacterial templated carbonate mineralization: insights from concave-type crystals induced by Curvibacter lanceolatus strain HJ-1.

The elucidation of carbonate crystal growth mechanisms contributes to a deeper comprehension of microbial-induced carbonate precipitation processes. In this research, the Curvibacter lanceolatus HJ-1 strain, well-known for its proficiency in inducing carbonate mineralization, was employed to trigger the formation of concave-type carbonate minerals. The study meticulously tracked the temporal alterations in the culture solution and conducted comprehensive analyses of the precipitated minerals' mineralogy and morphology using advanced techniques such as X-ray diffraction, scanning electron microscopy, focused ion beam, and transmission electron microscopy. The findings unequivocally demonstrate that concave-type carbonate minerals are meticulously templated by bacterial biofilms and employ calcified bacteria as their fundamental structural components. The precise morphological evolution pathway can be delineated as follows: initiation with the formation of bacterial biofilms, followed by the aggregation of calcified bacterial clusters, ultimately leading to the emergence of concave-type minerals characterized by disc-shaped, sunflower-shaped, and spherical morphologies.

Biochar-derived dissolved organic matter enhanced the release of residual ciprofloxacin from the soil solid phase.

Biochar has been utilized to reduce ciprofloxacin (CIP) residues in soil. However, little is known about the effect of biochar-derived dissolved organic matter (DOM) on residual CIP transformation. Thus, we analyzed the residual soil CIP as influenced by biochar generated from rice straw (RS3 and RS6), pig manure (PM3 and PM6), and cockroach shell (CS3 and CS6) at 300 °C and 600 °C. The three-dimensional excitation-emission matrix (3D-EEM), parallel factor analysis (PARAFAC) and two-dimensional correlation spectral analysis (2D-COS) were used to describe the potential variation in the DOM-CIP interaction. Compared with CK, biochar amendment increased the water-soluble CIP content by 160.7% (RS3), 55.2% (RS6), 534.1% (PM3), 277.5% (PM6), 1160.6% (CS3) and 703.9% (CS6), indicating that the biochar feedstock controlled the soil CIP release. The content of water-soluble CIP was positively correlated with the content of dissolved organic carbon (r = 0.922, p < 0.01) and dissolved organic nitrogen (r = 0.898, p < 0.01), suggesting that the major influence of the water-soluble CIP increase was DOM. The fluorescence quenching experiment showed that the interaction between DOM and CIP triggered static quenching and the creation of a DOM complex. The mean log K of protein-like material (4.977) was higher than that of terrestrial humus-like material (3.491), suggesting that the protein-like material complexed CIP was more stable than the humus-like material. Compared with pyrolysis at 300 °C, pyrolysis at 600 °C decreased the stability of the complex of protein-like material and CIP by 0.44 (RS), 1.689 (PM) and 0.548 (CS). This result suggested that the influence of temperature change was more profound on PM biochar-derived DOM than on RS and CS. These insights are essential for understanding CIP transportation in soil and controlling CIP contamination with biochar.

Mechanism of carbonate mineralization induced by microbes: Taking Curvibacter lanceolatus strain HJ-1 as an example.

Microbial-induced carbonate precipitation is important in the global carbon cycle, especially in fixing atmospheric CO2. Many simulation experiments have shown that microbes can induce carbonate precipitation, although there is no established understanding of the mechanism. In this study, several mineralization experiments were performed using Curvibacter lanceolatus strain HJ-1, including its secreted extracellular polymeric substances (EPS) and carbonic anhydrase (CA). We found that strain HJ-1, EPS, and CA could promote carbonate precipitation if compared with the respective control experiments (CK). Also, both HJ-1 and EPS1 experiments contained calcite and aragonite, whereas CA experiments formed calcite only. Therefore, HJ-1 and EPS is favorable for carbonate precipitation, especially for aragonite. Besides, the formation of calcite in the EPS2 experiments indicated that EPS contains a trace amount of CA, which might promote CO2 hydration and eventually lead to carbonate precipitation. It was suggested that CA only provide CO32- for the formation of carbonate minerals. In the absence of exogenous HCO3-, the optimized calcification rate followed the order: HJ-1(49.5 %) > CA(6.6 %) > EPS2(4.1 %). In addition, MICP mechanisms was studied, an increase in pH and CO2 hydration by CA play synergetic roles in providing supersaturated alkaline conditions in the system with bacteria. Finally, bacterial cells and EPS promote the formation of calcite and aragonite by acting as nucleation sites.