Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya.
Coral skeletons were long assumed to have a spherulitic structure, that is, a radial distribution of acicular aragonite (CaCO 3 ) crystals with their c-axes radiating from series of points, termed centers of calcification (CoCs). This assumption was based on morphology alone, not on crystallography. Here we measure the orientation of crystals and nanocrystals and confirm that corals grow their skeletons in bundles of aragonite crystals, with their caxes and long axes oriented radially and at an angle from the CoCs, thus precisely as expected for feather-like or "plumose" spherulites. Furthermore, we find that in both synthetic and coral aragonite spherulites at the nanoscale adjacent crystals have similar but not identical orientations, thus demonstrating by direct observation that even at nanoscale the mechanism of spherulite formation is non-crystallographic branching (NCB), as predicted by theory. Finally, synthetic aragonite spherulites and coral skeletons have similar angle spreads, and angular distances of adjacent crystals, further confirming that coral skeletons are spherulites. This is important because aragonite grows anisotropically, 10 times faster along the c-axis than along the a-axis direction, and spherulites fill space with crystals growing almost exclusively along the c-axis, thus they can fill space faster than any other aragonite growth geometry, and create isotropic materials from anisotropic crystals. Greater space filling rate and isotropic mechanical behavior are key to the skeleton's supporting function and therefore to its evolutionary success. In this sense, spherulitic growth is Nature's 3D printing. KEYWORDS: Ion attachment, crystallization by particle attachment, CPA, biomineralization, PEEM, PIC-mapping, mesocrystal S pherulites are polycrystalline structures in which acicular crystals radiate from a common center and grow approximately synchronously so the final shape of a spherulite resembles a sphere. 1−7 Figure 1 shows two types of spherulites: "spherical spherulite", in which the crystal fibers start from a point, or "plumose spherulite", in which crystal fibers radiate at an angle from the line. 7 Spherulites start forming as an aggregate of parallel acicular crystals termed "fibers", then form a "sheaf of wheat" structure, and with the growth of more fibers eventually become complete spheres. 8 In an ideal spherulite, fibers radiate from the center and contain all possible orientations within the sphere. Since the fast-growing axis in aragonite (CaCO 3 ) is the c-axis, 9 in spherulites each fiber elongation direction coincides with the crystalline c-axis. 10,11 In real spherulites, biogenic 12 and synthetic, 7 the crystal orientations are not perfectly radial nor continuously varying with angle, they deviate slightly from radial and exhibit small but abrupt changes in orientation, termed "branching". In Figure 1 branching angles are smaller than 30°in direction and in crystal lattice orientation. This is distinct from crystallographic branching, which occurs in sno...
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