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Minerals 2018, 8(8), 315;

Biomineral Reactivity: The Kinetics of the Replacement Reaction of Biological Aragonite to Apatite

Department für Geo-und Umweltwissenschaften, Ludwig-Maximilians-Universität, 80333 Munich, Germany
Departamento de Mineralogía y Petrología, Universidad Complutense de Madrid, 28040 Madrid, Spain
Instituto de Geociencias (IGEO), (UCM, CSIC), Ciudad Universitaria, 28040 Madrid, Spain
Central Facility for Electron Microscopy, University of Ulm, Albert-Einstein-Allee 11, 89069 Ulm, Germany
Instituto de Ciencia de Materiales de Madrid (ICMM, CSIC), Cantoblanco, 28049 Madrid, Spain
Author to whom correspondence should be addressed.
Received: 18 June 2018 / Revised: 16 July 2018 / Accepted: 20 July 2018 / Published: 26 July 2018
(This article belongs to the Special Issue Mineral Surface Reactions at the Nanoscale)
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We present results of bioaragonite to apatite conversion in bivalve, coral and cuttlebone skeletons, biological hard materials distinguished by specific microstructures, skeletal densities, original porosities and biopolymer contents. The most profound conversion occurs in the cuttlebone of the cephalopod Sepia officinalis, the least effect is observed for the nacreous shell portion of the bivalve Hyriopsis cumingii. The shell of the bivalve Arctica islandica consists of cross-lamellar aragonite, is dense at its innermost and porous at the seaward pointing shell layers. Increased porosity facilitates infiltration of the reaction fluid and renders large surface areas for the dissolution of aragonite and conversion to apatite. Skeletal microstructures of the coral Porites sp. and prismatic H. cumingii allow considerable conversion to apatite. Even though the surface area in Porites sp. is significantly larger in comparison to that of prismatic H. cumingii, the coral skeleton consists of clusters of dense, acicular aragonite. Conversion in the latter is sluggish at first as most apatite precipitates only onto its surface area. However, the process is accelerated when, in addition, fluids enter the hard tissue at centers of calcification. The prismatic shell portion of H. cumingii is readily transformed to apatite as we find here an increased porosity between prisms as well as within the membranes encasing the prisms. In conclusion, we observe distinct differences in bioaragonite to apatite conversion rates and kinetics depending on the feasibility of the reaction fluid to access aragonite crystallites. The latter is dependent on the content of biopolymers within the hard tissue, their feasibility to be decomposed, the extent of newly formed mineral surface area and the specific biogenic ultra- and microstructures. View Full-Text
Keywords: bioaragonite; apatite; microstructure; dissolution-reprecipitation; mineral replacement bioaragonite; apatite; microstructure; dissolution-reprecipitation; mineral replacement

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Greiner, M.; Férnandez-Díaz, L.; Griesshaber, E.; Zenkert, M.N.; Yin, X.; Ziegler, A.; Veintemillas-Verdaguer, S.; Schmahl, W.W. Biomineral Reactivity: The Kinetics of the Replacement Reaction of Biological Aragonite to Apatite. Minerals 2018, 8, 315.

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