Ultrastructural features of bacterial calcite unveil ubiquitous organics occlusion and clues on biomineralization

Abstract

Microbially-induced calcium carbonate precipitation is a widespread natural phenomenon with numerous technical applications. Recent advances have shown that bacterial calcium carbonates (BCC) form non-classically via amorphous calcium carbonate (ACC) precursors in the presence of organics, but the role of organics in the formation and nanostructural features of BCCs is not fully understood. Here we show that two bacterial strains produce BCCs with diverse textural and structural features at the macroscale but similar at the micro and nanoscale. We show that bacterial organics guide precipitation of calcite, stabilizing ACC to produce nanogranular crystals and these organics are then trapped within the crystal, rather than being released as previously suggested. These organics are N-rich and create regions of low Z-contrast aligned perpendicular to the c-axis of the crystal, yielding a "Swiss cheese-like" mesostructure. Moreover, it is these occluded organics that lead to the distinctive biosignatures observed in BCC. Finally, we also observe crystalline 2D-films, possibly proteins, templating the oriented crystallization of calcite. These ultrastructural features help to disclose how microbial CaCO3 biomineralization takes place leading to improved technical applications and may provide fingerprints for their identification in nature.