Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation.

Branson, Oscar and Bonnin, Elisa A and Perea, Daniel E and Spero, Howard J and Zhu, Zihua and Winters, Maria and Hönisch, Bärbel and Russell, Ann D and Fehrenbacher, Jennifer S and Gagnon, Alexander C (2016) Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation. Proceedings of the National Academy of Sciences of the United States of America, 113 (46). pp. 12934-12939. ISSN 0027-8424 Online ISSN 1091-6490 DOI https://doi.org/10.1073/pnas.1522864113

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Official URL: http://www.ncbi.nlm.nih.gov/pubmed/27794119

Abstract

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 à ngström-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.

Item Type: Article
Uncontrolled Keywords: NILAREP
Subjects: 01 - Climate Change and Earth-Ocean Atmosphere Systems
Divisions: 01 - Climate Change and Earth-Ocean Atmosphere Systems
Journal or Publication Title: Proceedings of the National Academy of Sciences of the United States of America
Volume: 113
Page Range: pp. 12934-12939
Identification Number: https://doi.org/10.1073/pnas.1522864113
Depositing User: Sarah Humbert
Date Deposited: 13 Dec 2019 17:29
Last Modified: 13 Dec 2019 17:29
URI: http://eprints.esc.cam.ac.uk/id/eprint/4597

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