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The Bivalve Shells Pinctada Fucata and Anodonta Cygnea and the Gastropod Shell Phorcus Turbinatus

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The Bivalve Shells Pinctada Fucata and Anodonta Cygnea and the Gastropod Shell Phorcus Turbinatus COMPARISON OF THE MICROSTRUCTURE OF THE BIVALVE SHELLS PINCTADA FUCATA AND ANODONTA CYGNEA AND THE GASTROPOD SHELL PHORCUS TURBINATUS Dissertation Zur Erlangung des Dokt or grades an der Fakultät für Mathematik, Informatik und Naturwissenschaften im Fachbereich Geowissenschaften der Universität Hamburg vorgelegt von J i anhan He aus J i ngzhou, P.R.C hi na Hamburg, 2018 Vorsitzende/r: Prof. Dr. Ulrich Bismayer Erstgutachter: Prof. Dr. Ulrich Bismayer Zweitgutachter: Prof. Dr. Jochen Schlüter Datum der Disputation: 05. Juni 2018 Eidesstattliche Versicherung Declaration on oath according to § 7 (4) doctoral degree regulations of MIN faculty Hiermit erkläre ich an Eides statt, dass ich die vorliegende Dissertationsschrift selbst verfasst und keine anderen als die angegebenen Quellen und Hilfsmittel benutzt habe. I hereby declare, on oath, that I have written the present dissertation by my own and have not used other than the acknowledged resources and aids. Hamburg 27.03.2018 Hamburg, den / city and date Unterschrift / signature ‘Many years later as he faced the firing squad, Colonel Aureliano Buendía was to remember that distant afternoon when his father took him to discover ice.’ Gabriel García Márquez, One Hundred Years of Solitude. For my father Shunyou He and my mother Zhengxiang Lei. C OMPARISON OF THE MIC ROSTRUCTURE OF THE B IVALVE SHELLS P INCTADA FUCATA A N D A NODONTA CYGNEA AND THE GASTROPOD SH E L L P HORCUS TURBINATUS Content Content Abstract ..................................................................................................................................... 3 1 Introduction ....................................................................................................................... 7 1.1 Biominerals and biomineralization ............................................................................ 7 1.1.1 Species of biominerals ................................................................................... 8 1.1.2 Biominerals and organic matrix in molluscs .................................................. 9 1.1.3 Studies of biominerals based on EBSD and Raman spectroscopy .............. 12 1.2 Molluscs ................................................................................................................... 16 1.2.1 Bivalvia ........................................................................................................ 16 1.2.2 Gastropoda ................................................................................................... 19 1.3 Calcium carbonates .................................................................................................. 23 1.3.1 Calcite .......................................................................................................... 23 1.3.2 Aragonite ...................................................................................................... 24 2 Materials and methods .................................................................................................... 26 2.1 Samples and sample preparation .............................................................................. 26 2.2 Scanning electron microscopy (SEM) ..................................................................... 30 2.3 Electron backscatter diffraction ............................................................................... 31 2.4 Laser Raman spectroscopy....................................................................................... 33 2.5 Electron microprobe ................................................................................................. 38 3 Results ............................................................................................................................... 39 3.1 Morphology of samples ........................................................................................... 39 3.1.1 Pinctada fucata ............................................................................................ 39 3.1.2 Anodonta cygnea .......................................................................................... 42 3.1.3 Phorcus turbinatus ....................................................................................... 45 3.2 Crystallography orientation of samples ................................................................... 48 3.2.1 Pinctada fucata ............................................................................................ 48 3.2.2 Anodonta cygnea .......................................................................................... 55 3.2.3 Phorcus turbinatus ....................................................................................... 70 3.3 Chemical composition of samples ........................................................................... 76 3.3.1 Pinctada fucata ............................................................................................ 76 1 C OMPARISON OF THE MIC ROSTRUCTURE OF THE B IVALVE SHELLS P INCTADA FUCATA A N D A NODONTA CYGNEA AND THE GASTROPOD SH E L L P HORCUS TURBINATUS Content 3.3.2 Anodonta cygnea .......................................................................................... 80 3.3.3 Phorcus turbinatus ....................................................................................... 84 4 Discussion ......................................................................................................................... 89 4.1 Nacreous layers ........................................................................................................ 89 4.2 Prismatic layers ........................................................................................................ 94 4.3 From prisms to nacre ............................................................................................... 99 5 Conclusions .................................................................................................................... 101 Bibliography .......................................................................................................................... 103 Appendix ............................................................................................................................... 113 Appendix I ....................................................................................................................... 113 Appendix II ...................................................................................................................... 115 Appendix III .................................................................................................................... 116 Appendix IV .................................................................................................................... 117 Appendix V ..................................................................................................................... 118 Appendix VI .................................................................................................................... 119 Curriculum Vitae .................................................................................................................. 120 List of publications ............................................................................................................... 122 Acknowledgements ............................................................................................................... 123 2 C OMPARISON OF THE MIC ROSTRUCTURE OF THE B IVALVE SHELLS P INCTADA FUCATA A N D A NODONTA CYGNEA AND THE GASTROPOD SH E L L P HORCUS TURBINATUS Abstract Abstract The structure of mollusc shells is of major interest in the field of biomineral research due to its potential application in bionic materials. In order to understand the physical/chemical background of their outstanding biomechanical properties, in this study topological and material features were revealed using several morphological, crystal orientational and spectroscopic methods. Three shells from different habitats were selected as the main experimental subjects: a bivalve named Pinctada fucata from South China Sea, another bivalve named Anodonta cygnea from the Volga River in Russia and a gastropod Phorcus turbinatus from the Mediterranean Sea on the coast of France. By applying scanning electron microscope, the structures of the shells were studied in detail. By using electron backscatter diffraction and Raman spectroscopy, the variation of the crystal orientation in different crystallites was investigated comprehensively. Furthermore, microprobe and electron microscopy provided insight into the compositional and morphological differences between the three species. Shells of the three species have similar mesoscopic structure, which consists of two types of layers: nacreous layer and prismatic layer. From the crystallographic arrangement, such as the distribution of domain structure and mesoscale twining, differences of nacreous layers in three species were compared. Based on differences in compositions, mesostructures and crystallographic features, the structural information of prismatic layers is enhanced. Finally, the transition between two layers and possible growth modes have been discussed in this work. In the three species, the inner part of the shell is an aragonitic nacreous layer composed of nacre tablets in ‘brick-and-mortar’ arrangement. The c-axis of aragonite crystallites of the three species has identical orientation, the a- or b-axis is however arranged in different domain structures. Cross sections of all
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