Plankton, corals, and other organisms produce calcium carbonate skeletons that are integral to their survival, form a key component of the global carbon cycle, and record an archive of past oceanographic conditions in their geochemistry. A key aspect of the formation of these biominerals is the interaction between organic templating structures and mineral precipitation processes. Laboratory-based studies have shown that these atomic-scale processes can profoundly influence the architecture and composition of minerals, but their importance in calcifying organisms is poorly understood because it is difficult to measure the chemistry of in vivo biomineral interfaces at spatially relevant scales. Understanding the role of templates in biomineral nucleation, and their importance in skeletal geochemistry requires an integrated, multiscale approach, which can place atom-scale observations of organic-mineral interfaces within a broader structural and geochemical context. Here we map the chemistry of an embedded organic template structure within a carbonate skeleton of the foraminifera Orbulina universa using both atom probe tomography (APT), a 3D chemical imaging technique with Ångström-level spatial resolution, and time-of-flight secondary ionization mass spectrometry (ToF-SIMS), a 2D chemical imaging technique with submicron resolution. We quantitatively link these observations, revealing that the organic template in O. universa is uniquely enriched in both Na and Mg, and contributes to intraskeletal chemical heterogeneity. Our APT analyses reveal the cation composition of the organic surface, offering evidence to suggest that cations other than Ca 2+ , previously considered passive spectator ions in biomineral templating, may be important in defining the energetics of carbonate nucleation on organic templates. biomineralization | templating | foraminifera | geochemistry | paleoceanography
The calcium carbonate shells of planktic foraminifera provide our most valuable geochemical archive of ocean surface conditions and climate spanning the last 100 million years, and play an important role in the ocean carbon cycle. These shells are preserved in marine sediments as calcite, the stable polymorph of calcium carbonate. Here, we show that shells of living planktic foraminifers Orbulina universa and Neogloboquadrina dutertrei originally form from the unstable calcium carbonate polymorph vaterite, implying a non-classical crystallisation pathway involving metastable phases that transform ultimately to calcite. The current understanding of how planktic foraminifer shells record climate, and how they will fare in a future high-CO2 world is underpinned by analogy to the precipitation and dissolution of inorganic calcite. Our findings require a re-evaluation of this paradigm to consider the formation and transformation of metastable phases, which could exert an influence on the geochemistry and solubility of the biomineral calcite.
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