Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule
Edited by Jack Halpern, University of Chicago, Chicago, IL, and approved September 25, 2008
Abstract
Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40–200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism.
Acknowledgments.
We thank Prof. Peter Rez for fruitful discussions. This work was supported by National Science Foundation Award CHE&DMR-0613972 (to P.G.), Department of Energy Award DE-FG02-07ER15899 (to P.G. and S.W.), and Israel Ministry of Science Project 777. The experiments were performed at the University of Wisconsin–Synchrotron Radiation Center, which was supported by National Science Foundation Award DMR-0537588. F.H.W. is supported by the National Institutes of Health and National Science Foundation. L.A. is the incumbent of the Dorothy and Patrick Gorman Professorial Chair of Biological Ultrastructure, and S.W. is the incumbent of the Dr. Walter and Dr. Trude Burchardt Professorial Chair of Structural Biology. I.S. is the incumbent of the Pontecorvo Professorial Chair of Cancer Research.
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© 2008 by The National Academy of Sciences of the USA.
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Received: July 8, 2008
Published online: November 11, 2008
Published in issue: November 11, 2008
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Acknowledgments
We thank Prof. Peter Rez for fruitful discussions. This work was supported by National Science Foundation Award CHE&DMR-0613972 (to P.G.), Department of Energy Award DE-FG02-07ER15899 (to P.G. and S.W.), and Israel Ministry of Science Project 777. The experiments were performed at the University of Wisconsin–Synchrotron Radiation Center, which was supported by National Science Foundation Award DMR-0537588. F.H.W. is supported by the National Institutes of Health and National Science Foundation. L.A. is the incumbent of the Dorothy and Patrick Gorman Professorial Chair of Biological Ultrastructure, and S.W. is the incumbent of the Dr. Walter and Dr. Trude Burchardt Professorial Chair of Structural Biology. I.S. is the incumbent of the Pontecorvo Professorial Chair of Cancer Research.
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This article is a PNAS Direct Submission.
This article contains supporting information online at www.pnas.org/cgi/content/full/0806604105/DCSupplemental.
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The authors declare no conflict of interest.
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Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule, Proc. Natl. Acad. Sci. U.S.A.
105 (45) 17362-17366,
https://doi.org/10.1073/pnas.0806604105
(2008).
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