Biomineral Reactivity: The Kinetics of the Replacement Reaction of Biological Aragonite to Apatite
Abstract
:1. Introduction
2. Materials and Methods
2.1. Test Materials
2.2. Experimental Setup
2.3. Organic Matrix Preparation by Selective Etching
2.4. Characterization Methods
3. Results
3.1. X-Ray Diffraction Analysis
3.2. FTIR-Spectroscopy
3.3. Scanning Electron Microscopy (SEM)
4. Discussion
4.1. The Phase Conversion Mechanism
4.2. The Conversion of Geologic Aragonite
4.3. The Conversion of Biologic Aragonites
4.3.1. Sepia officinalis Cuttlebone Aragonite
4.3.2. Porites sp. Acicular and Hyriopsis cumingii Prismatic Aragonite
4.3.3. Arctica islandica Cross-Lamellar and Hyriopsis cumingii Nacreous Aragonite
5. Conclusions
- We find highly distinct rates and kinetics of conversion to apatite for the selected aragonitic biological hard tissues. This is dependent on the ability of the reaction fluid to access aragonite crystallites, which directly relates to the content and the extent of decomposition of biopolymers within the hard tissue, the extent of the newly formed surface area and the specific biological hard tissue macro- and microstructures.
- When treated for up to, respectively, 1 and 14 days, a profound conversion of bioaragonite to apatite within mineral units and/or structural elements takes place in the cuttlebone of the cephalopod Sepia officinalis and in the prismatic columns of the bivalve Hyriopsis cumingii.
- Conversion of Sepia officinalis aragonite occurs almost instantly. It is highly accelerated at the beginning and slows down towards the end of the conversion process.
- Conversion to AP in Hyriopsis cumigii prisms is steadily increasing for almost the entire time span of the experiment. However, the process stagnates for the final stages of the experiment.
- Even though having a large surface area given by the specific macrostructure, the acicular microstructure of the warm water coral Porites sp. gives a compact hard tissue. At the start of the conversion process only outer skeletal surfaces are subject to dissolution and conversion to AP. With progressive conversion, apatite formation accelerates quickly when the fluid enters the skeleton through the centers of calcification.
- The cross-lamellar microstructure in Arctica islandica is, at first, highly resistant to phase conversion. It speeds slightly up when the network of organic biopolymers becomes destroyed, and the reaction fluid can permeate the entire hard tissue. The presence of pores within outer shell layers facilitates fluid infiltration even further and accelerates even more the conversion process for this part of the shell.
- Nacreous aragonite in Hyriopsis cumingii is most resistant to conversion. Even though nacre tablets are encased by organic membranes, the latter are not decomposed easily, thus the aragonite of the nacreous shell layer is not attacked and remains intact.
- All aragonite biominerals transform into AP at a much faster rate than geological aragonite. Hyriopsis cumingii nacre is the biomaterial that shows a conversion kinetics that resembles that of geologic aragonite most closely. This is consistent with the resistance to degradation of organic membranes in the former.
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
Appendix A
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AP Content (wt %) after 4 Days | AP Content (wt %) after 7 Days | AP Content (wt %) after 9 Days | AP Content (wt %) after 14 Days | ||||
Porites sp. | 12.0(4) | 13.8(3) | 12.7(3) | 38(1) | |||
Hyriopsis cumingii (nacre) | < 1 | < 1 | < 1 | < 1 | |||
Hyriopsis cumingii (prismatic aragonite) | 7.2(4) | 16.4(8) | 24.8(9) | 25.8(9) | |||
Arctica islandica (shell layer next to seawater) | 1.9 | 2.1 | 9.5(4) | 17.6(5) | |||
Arctica islandica (shell layer next to soft tissue) | 2.5 | 2.4 | 9.6(7) | 11.4(4) | |||
geologic aragonite (single crystal) | not determined | 1.4 | not determined | 3.1 | |||
AP Content (wt %) after 1 Hour | AP Content (wt %) after 3 Hours | AP Content (wt %) after 5 Hours | AP Content (wt %) after 8 Hours | AP Content (wt %) after 24 Hours | |||
Sepia officinalis | 29.9(7) | 58.2(8) | 64.4(7) | 74.5(8) | 99(1) |
0–4 Days | 4–7 Days | 7–9 Days | 9–14 Days | |||||
Acicular aragonite Porites sp. | very strong increase | no change | no change | very strong increase | ||||
Prismatic aragonite H. cumingii | strong increase | very strong increase | very strong increase | no change | ||||
Cross-lamellar aragonite A. islandica outer layer | slight increase | no change | very strong increase | strong increase | ||||
Cross-lamellar aragonite A. islandica inner layer | slight increase | no change | very strong increase | no change | ||||
Nacreous aragonite H. cumingii | no change | no change | no change | no change | ||||
Geologic aragonite single crystal | - | no change | - | slight increase | ||||
0–1 Hour | 1–3 Hours | 3–5 Hours | 5–8 Hours | 8–24 Hours | ||||
Granular aragonite Sepia officinalis | very strong increase | very strong increase | slight increase | strong increase | very strong increase |
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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. https://doi.org/10.3390/min8080315
Greiner M, Férnandez-Díaz L, Griesshaber E, Zenkert MN, Yin X, Ziegler A, Veintemillas-Verdaguer S, Schmahl WW. Biomineral Reactivity: The Kinetics of the Replacement Reaction of Biological Aragonite to Apatite. Minerals. 2018; 8(8):315. https://doi.org/10.3390/min8080315
Chicago/Turabian StyleGreiner, Martina, Lurdes Férnandez-Díaz, Erika Griesshaber, Moritz N. Zenkert, Xiaofei Yin, Andreas Ziegler, Sabino Veintemillas-Verdaguer, and Wolfgang W. Schmahl. 2018. "Biomineral Reactivity: The Kinetics of the Replacement Reaction of Biological Aragonite to Apatite" Minerals 8, no. 8: 315. https://doi.org/10.3390/min8080315