A nanocrystalline monoclinic CaCO3 precursor of metastable aragonite.

ABSTRACT: Despite its thermodynamical metastability at near-surface conditions, aragonite is widespread in marine and terrestrial sediments. It abundantly forms in living organisms, and its abiotic formation is favored in waters of a Mg2+/Ca2+ ratio > 1.5. Here, we provide crystallographic evidence of a nanocrystalline CaCO3 polymorph, which precipitates before aragonite in a cave. The new phase, which we term monoclinic aragonite (mAra), is crystallographically related to ordinary, orthorhombic aragonite. Electron diffraction tomography combined with structure determination demonstrates that mAra has a layered aragonite structure, in which some carbonates can be replaced by hydroxyls and up to 10 atomic % of Mg can be incorporated. The diagnostic electron diffraction features of mAra are diffuse scattering and satellite reflections along aragonite {110}. Similar features have previously been reported-although unrecognized-from biogenic aragonite formed in stromatolites, mollusks, and cyanobacteria as well as from synthetic material. We propose that mAra is a widespread crystalline CaCO3 that plays a hitherto unrecognized key role in metastable aragonite formation.

SUBMITTER: Nemeth P 

PROVIDER: S-EPMC6291313 | biostudies-literature | 2018 Dec

REPOSITORIES: biostudies-literature