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The fibrous calcite layer of modern brachiopod shells is a hybrid composite material and forms a substantial part of the hard tissue. We investigated how cells of the outer mantle epithelium (OME) secrete calcite material and generate the characteristic fibre morphology and composite microstructure of the shell. We employed AFM, FE-SEM, and TEM imaging of embedded/etched, chemically fixed/decalcified and high-pressure frozen/freeze substituted samples. Calcite fibres are secreted by outer mantle epithelium (OME) cells. Biometric analysis of TEM micrographs indicates that about 50% of these cells are attached via hemidesmosomes to an extracellular organic membrane present at the proximal, convex surface of the fibres. At these sites, mineral secretion is not active. Instead, ion transport from OME cells to developing fibres occurs at regions of closest contact between cells and fibres, however only at sites where the extracellular membrane at the proximal fibre surface is not developed yet. Fibre formation requires the cooperation of several adjacent OME cells. It is a spatially and temporally changing process comprising of detachment of OME cells from the extracellular organic membrane, mineral secretion at detachment sites, termination of secretion with formation of the extracellular organic membrane, and attachment of cells via hemidesmosomes to this membrane.

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Biological hard tissues are a rich source of design concepts for the generation of advanced materials. They represent the most important library of information on the evolution of life and its environmental conditions. Organisms produce soft and hard tissues in a bottom-up process, a construction principle that is intrinsic to biologically secreted materials. This process emerged early on in the geological record, with the onset of biological mineralization. The phylum Brachiopoda is a marine animal group that has an excellent and continuous fossil record from the early Cambrian to the Recent. Throughout this time interval, the Brachiopoda secreted phosphate and carbonate shells and populated many and highly diverse marine habitats. This required great flexibility in the adaptation of soft and hard tissues to the different marine environments and living conditions. This review presents, juxtaposes and discusses the main modes of mineral and biopolymer organization in Recent, carbonate shell-producing, brachiopods. We describe shell tissue characteristics for taxa of the orders Rhynchonellida, Terebratulida, Thecideida and Craniida. We highlight modes of calcite and organic matrix assembly at the macro-, micro-, and nano-scales based on results obtained by Electron Backscatter Diffraction, Atomic Force Microscopy, Field Emission Scanning Electron Microscopy and Scanning Transmission Electron Microscopy. We show variation in composite hard tissue organization for taxa with different lifestyles, visualize nanometer-scale calcite assemblies for rhynchonellide and terebratulide fibers, highlight thecideide shell microstructure, texture and chemistry characteristics, and discuss the feasibility to use thecideide shells as archives of proxies for paleoenvironment and paleoclimate reconstructions.

Abstract. Carbonate biological hard tissues are valuable archives of environmental information. However, this information can be blurred or even completely lost as hard tissues undergo diagenetic alteration. This is more likely to occur in aragonitic skeletons because bioaragonite often transforms into calcite during diagenesis. For reliably using aragonitic skeletons as geochemical proxies, it is necessary to understand in depth the diagenetic alteration processes that they undergo. Several works have recently investigated the hydrothermal alteration of aragonitic hard tissues during short-term experiments at high temperatures (T > 160 ∘C). In this study, we conduct long-term (4 and 6 months) hydrothermal alteration experiments at 80 ∘C using burial-like fluids. We document and evaluate the changes undergone by the outer and inner layers of the shell of the bivalve Arctica islandica, the prismatic and nacreous layers of the hard tissue of the gastropod Haliotis ovina, and the skeleton of the coral Porites sp. combining a variety of analytical tools (X-ray diffraction, thermogravimetry analysis, laser confocal microscopy, scanning electron microscopy, electron backscatter diffraction and atomic force microscopy). We demonstrate that this approach is the most adequate to trace subtle, diagenetic-alteration-related changes in aragonitic biocarbonate structural hard materials. Furthermore, we unveil that the diagenetic alteration of aragonitic biological hard tissues is a complex multi-step process where major changes occur even at the low temperature used in this study, well before any aragonite into calcite transformation takes place. Alteration starts with biopolymer decomposition and concomitant generation of secondary porosity. These processes are followed by abiogenic aragonite precipitation that partially or totally obliterates the secondary porosity. Only subsequently does the transformation of the aragonite into calcite occur. The kinetics of the alteration process is highly dependent on primary microstructural features of the aragonitic biomineral. While the skeleton of Porites sp. remains virtually unaltered for the entire duration of the conducted experiments, Haliotis ovina nacre undergoes extensive abiogenic aragonite precipitation. The outer and inner shell layers of Arctica islandica are significantly affected by aragonite transformation into calcite. This transformation is extensive for the prismatic shell layer of Haliotis ovina. Our results suggest that the majority of aragonitic fossil archives are overprinted, even those free of clear diagenetic alteration signs. This finding may have major implications for the use of these archives as geochemical proxies.

Thecideide brachiopods are an anomalous group of invertebrates. In this study, we discuss the evolution of thecideide brachiopods from the Triassic to the Holocene and base our results and conclusions on microstructure and texture measurements gained from electron backscatter diffraction (EBSD). In fossil and Recent thecideide shells, we observe the following mineral units: (1) nanometric to small granules; (2) acicles; (3) fibres; (4) polygonal crystals; and (5) large roundish crystals. We trace for thecideide shells the change of mineral unit characteristics such as morphology, size, orientation, arrangement and distribution pattern. Triassic thecideide shells contain extensive sections formed of fibres interspersed with large, roundish crystals. Upper Cretaceous to Pleistocene thecideide hard tissues consist of a matrix of minute to small grains reinforced by acicles and small polygonal crystals. Recent thecideide species form their shell of mineral units that show a wide range of shapes, sizes and arrangements. We find from Late Triassic to Recent a gradual decrease in mineral unit size, regularity of mineral unit morphology and orientation and the degree of calcite co‐orientation. While crystallite co‐orientation is the highest for fibrous microstructures, it is strikingly low for taxa that form their shell out of nanogranular to acicular mineral units. Our results indicate that Upper Jurassic species represent transitional forms between ancient taxa with fibrous shells and Recent forms that construct their shells of acicles and granules. We attribute the observed changes in microstructure and texture to be an adaptation to a different habitat and lifestyle associated with cementation to hard substrates.

Here, we provide the dataset associated with the research article “Orientation patterns of aragonitic crossed-lamellar, fibrous prismatic and myostracal microstructures of modern Glycymeris shells” [1]. Based on several tools (SEM, EBSD, laser confocal microscopy and FE-SEM) we present original data relative to the microstructure and texture of aragonite crystallites in all Glycymeris shell layers (crossed-lamellar, complex crossed-lamellar, fibrous prismatic and pedal retractor and adductor myostraca) and address texture characteristics at the transition from one layer to the other, identifying similarities and differences among the different layers. Shells were cut transversely, obliquely and longitudinally in order to obtain different orientated sections of the outer and inner layer and of the myostraca. The identification of major microstructural elements was provided by detailed SEM and laser confocal microscopy images. Microstructure and texture characterization was based on EBSD measurements presented as band contrast images and as color-coded crystal orientation maps with corresponding pole figures. Crystal co-orientation was measured with the MUD value. Finally, the distribution of the organic matrix occluded within the outer crossed-lamellar layer was revealed using FE-SEM. These data, besides providing a modern unaltered Glycymeris reference to detect diagenetic alteration in fossil analogs used for paleoenvironmental reconstructions, are useful to better comprehend the mechanisms of bivalve shell formation.