Prismatic Calcite Research Articles

The Biological Crystals in Chamid Bivalve Shells: Diversity in Morphology and Crystal Arrangement Pattern

Chamid bivalves are marine organisms that live in high-energy environments and are cemented to hard substrates. To avoid shell damage, the organisms form thick, densely ornamented shells. Shell material consists of aragonite, and the ornamentation may be either aragonitic or calcitic. The latter can be developed as scaly spines, rows of blades, or comarginal, radial arched lamellae. We investigated biological crystal morphology and mode of assembly of Chama arcana and Chama gryphoides shells. Structural characteristics were obtained from electron backscatter diffraction (EBSD) measurements, complemented with laser confocal and BSE imaging. We found a wide range of crystal morphologies and sizes, ranging from irregularly shaped calcite and/or aragonite prisms to tiny and thin aragonite laths. We observed four different modes of crystal assembly patterns: 1. strongly interlocked dendritic calcite units forming the ornamentation blades; 2. aragonite laths arranged to lamellae forming the outer shell layer, the layer adjacent to the calcite; 3. aragonite laths arranged into blocks comprising inner shell layers or aragonitic ornamentations; and 4. shell portions consisting of aragonite prisms, structured in size and crystal orientation, at muscle attachment sites. These four different types of crystal arrangements were observed for the shells of the investigated chamid species; however, they had slightly different strengths of structuring and slight variations in crystal organisation. Additionally, we observed unique microstructural features in Chama shells: We report ornamentation crystals resembling idiomorphic calcite and novel, twinned entities found at the changeover between the aragonitic layers. We highlight and discuss these differences and anomalies in this contribution.

Fingerprinting enhanced floodplain reworking during the Paleocene–Eocene Thermal Maximum in the Southern Pyrenees (Spain): Implications for channel dynamics and carbon burial

Abstract The sedimentary record of the Paleocene–Eocene Thermal Maximum (PETM, ca. 56 Ma) allows the study of feedback mechanisms over the entire duration of a climatic event, from carbon release to the subsequent recovery phase. Clay sedimentation increase in the oceans during the PETM is linked to enhanced terrestrial erosion. Fluvial channel mobility has been invoked to explain this increase in fine sediment export based on more frequent transitional avulsions. In this study, we test whether the reworking of Microcodium (prismatic calcite concretions) from the floodplain to marine environments can serve to fingerprint floodplain reworking due to channel mobility. We quantified the abundance of floodplain-sourced Microcodium grains reworked in fluvial to marine sandstones pre-dating and coeval to the PETM in the Southern Pyrenees (Tremp Basin, Spain). Laser ablation–inductively coupled plasma–mass spectrometry U-Pb ages on calcite confirm the Thanetian age of the Microcodium grains. Our data show a four-fold increase in the export of floodplain sediments to the marine domain during the PETM. Moreover, we show that this is predominantly due to enhanced channel mobility, reworking channel banks and interfluves, with increased erosion in the hinterland as a secondary factor. This increase in floodplain reworking would correspond to an increase in biospheric carbon burial flux by a factor of 2.2. Therefore, enhanced channel mobility and fine-grain sediment transport to the oceans during a climatic perturbation such as the PETM may constitute an important negative feedback mechanism.

EBSD analysis of twin boundaries of prismatic calcite in oyster shells

EBSD analysis of twin boundaries of prismatic calcite in oyster shells

Evidence of a Scheduled End for Prism Growth in the Shell of Pinctada margaritifera: Closure of the Calcite Biomineralization Area by a Specific Organic Membrane

The shell of the pearl oyster Pinctada margaritifera is made up of two layers: an outer layer of calcite prisms and an inner layer of aragonite tablets. Recent studies have shown that the calcite layer develops in a series of steps. We found that the end of prism growth and the start of aragonite deposition are also complex processes. Contrary to the common belief that prism growth is interrupted by the expansion of the aragonite layer, we found that a specific membrane covers the calcite surface before aragonite deposition starts. The earliest aragonite depositions occur as granular spots located only on the surfaces covered by this organic membrane This membrane appears to be the final stage of the calcite biomineralization cycle. This new understanding of calcite development has implications for shell biomineralization research and the production of pearls.

Microbialites on the northern shelf of Lake Van, eastern Türkiye#: Morphology, texture, stable isotope geochemistry and age

ABSTRACTLake Van, the world's largest alkaline lake, hosts some of the largest microbialite towers worldwide, which are considered as modern analogues of ancient stromatolites. This study investigates the links between microbialite evolution, geology, climate and hydrology, and the role of biotic and abiotic processes in microbialite growth and morphology. For these objectives, the northern shelf of Lake Van was surveyed by sub‐bottom seismic profiling and diving, and two 9 m and 15 m high microbialite chimneys were sampled at 25 m water depth. Samples were analysed for stable oxygen and carbon isotopes, X‐ray diffractometry, scanning electron microscopy and U/Th age dating. Lake Van microbialites precipitate wherever focused Ca‐rich groundwater flows onto the lake floor to mix with alkaline lake water. Variable columnar, conical and branching morphologies of the microbialites indicate various processes of formation by groundwater channelling within the chimneys. Collectively, our data suggest that the microbialite chimneys have formed within the last millennium, most likely starting during the warm and humid Medieval Climate Anomaly (ca ad 800–1300), when lake level rose approximately to the present level due to enhanced Inputs of riverine Ca‐rich freshwater and groundwater. Our new scanning electron microscopy observations indicate that the internal structure of the microbialites below the outer cyanobacteria‐covered crust is constructed by calcified filaments, globular aggregates and nanocrystals of algal, cyanobacterial and heterobacterial origins and inorganically precipitated prismatic calcite crystals. These textural features, together with dive observations, clearly demonstrate the important role of inorganic carbonate precipitation at sites of groundwater discharge, followed by cyanobacteria and algal mucilage deposition and microbially meditated calcification in the photic zone in the rapid growth of the microbialite chimneys. Considering the close similarities of some textures with those of ancient stromatolites and meteorites, the results of this study provide new insights into the environmental conditions associated with stromatolite formation and extra‐terrestrial life evolution.

In situ mapping of biomineral skeletal proteins by molecular recognition imaging with antibody-functionalized AFM tips.

Spatial localizing of skeletal proteins in biogenic minerals remains a challenge in biomineralization research. To address this goal, we developed a novel in situ mapping technique based on molecular recognition measurements via atomic force microscopy (AFM), which requires three steps: (1) the development and purification of a polyclonal antibody elicited against the target protein, (2) its covalent coupling to a silicon nitride AFM tip ('functionalization'), and (3) scanning of an appropriately prepared biomineral surface. We applied this approach to a soluble shell protein - accripin11 - recently identified as a major component of the calcitic prisms of the fan mussel Pinna nobilis [1]. Multiple tests reveal that accripin11 is evenly distributed at the surface of the prisms and also present in the organic sheaths surrounding the calcitic prisms, indicating that this protein is both intra- and inter-crystalline. We observed that the adhesion force in transverse sections is about twice higher than in longitudinal sections, suggesting that accripin11 may exhibit preferred orientation in the biomineral. To our knowledge, this is the first time that a protein is localized by molecular recognition atomic force microscopy with antibody-functionalized tips in a biogenic mineral. The 'pros' and 'cons' of this methodology are discussed in comparison with more 'classical' approaches like immunogold. This technique, which leaves the surface to analyze clean, might prove useful for clinical tests on non-pathological (bone, teeth) or pathological (kidney stone) biomineralizations. Studies using implants with protein-doped calcium phosphate coating can also benefit from this technology. STATEMENT OF SIGNIFICANCE: Our paper deals with an unconventional technical approach for localizing proteins that are occluded in biominerals. This technique relies on the use of molecular recognition atomic force microscopy with antibody-functionalized tips. Although such approach has been employed in other system, this is the very first time that it is developed for biominerals. In comparison to more classical approaches (such as immunogold), AFM microscopy with antibody-functionalized tips allows higher magnification and keeps the scanned surface clean for other biophysical characterizations. Our method has a general scope as it can be applied in human health, for non-pathological (bone, teeth) and pathological (kidney stone) biomineralizations as well as for bone implants coated with protein-doped calcium phosphate.

Calcite Twinning in Mollusk Shells and Carrara Marble

AbstractMollusk shells protect the animals that form and inhabit them. They are composites of minerals and organics, with diverse mesostructures, including nacre, prismatic calcite, crossed‐lamellar aragonite, and foliated calcite. Twins, that is, crystals mirror symmetric with respect to their coherent interface, occurring as formation or deformation twins, are observed in all mollusk shell mesostructures but never within calcite prisms. Here, nanotwins and microwins within single calcite prisms are observed in different shells. Using Polarization‐dependent Imaging Contrast (PIC) mapping with 20–60 nm resolution, twins are observed to be 0.2–3 µm thick layers of differently oriented and colored crystals with respect to the main prism crystal. Multiple twins are interspersed with the prism crystal, parallel to one another, and similarly oriented. When comparing images of calcite prisms and twins obtained by PIC mapping and by Electron Back‐Scattered Diffraction (EBSD), the images correspond precisely. All twins are e‐twin types, with 127° angular distance between c‐axes. E‐twins are the most common deformation twins in geologic calcite, as also observed here in Carrara marble. Location of all twins near the outer surface of all shells and e‐twin type both suggest that twins within calcite prisms in mollusk shells result from deformation twinning.

Calcitic Prisms of The Giant Seashell Pinna Nobilis Form Light Guide Arrays.

The shells of the Pinnidae family are based on a double layer of single-crystal-like calcitic prisms and inner aragonitic nacre, a structure known for its outstanding mechanical performance. However, on the posterior side, shells are missing the nacreous layer, which raises the question of whether there canbe any functional role in giving up this mechanical performance. Here, it isdemonstrated that the prismatic part of the Pinna nobilis shell exhibits unusual optical properties, whereby each prism acts as an individual optical fiber guiding the ambient light to the inner shell cavity by total internal reflection. This pixelated light channeling enhances both spatial resolution and contrast while reducing angular blurring, an apt combination for acute tracking of a moving object. Thesefindings offer insights into the evolutionary aspects of light-sensing and imaging and demonstrate how an architectured optical system for efficient light-tracking can be based on birefringent ceramics.

Fibrous or Prismatic? A Comparison of the Lamello-Fibrillar Nacre in Early Cambrian and Modern Lophotrochozoans.

The Precambrian-Cambrian interval saw the first appearance of disparate modern metazoan phyla equipped with a wide array of mineralized exo- and endo-skeletons. However, the current knowledge of this remarkable metazoan skeletonization bio-event and its environmental interactions is limited because uncertainties have persisted in determining the mineralogy, microstructure, and hierarchical complexity of these earliest animal skeletons. This study characterizes in detail a previously poorly understood fibrous microstructure-the lamello-fibrillar (LF) nacre-in early Cambrian mollusk and hyolith shells and compares it with shell microstructures in modern counterparts (coleoid cuttlebones and serpulid tubes). This comparative study highlights key differences in the LF nacre amongst different lophotrochozoan groups in terms of mineralogical compositions and architectural organization of crystals. The results demonstrate that the LF nacre is a microstructural motif confined to the Mollusca. This study demonstrates that similar fibrous microstructure in Cambrian mollusks and hyoliths actually represent a primitive type of prismatic microstructure constituted of calcitic prisms. Revision of these fibrous microstructures in Cambrian fossils demonstrates that calcitic shells are prevalent in the so-called aragonite sea of the earliest Cambrian. This has important implications for understanding the relationship between seawater chemistry and skeletal mineralogy at the time when skeletons were first acquired by early lophotrochozoan biomineralizers.

An approach to improve compressive strength of cement paste at low temperature by carbonation curing

Portland cement showed a lower hydration rate and compressive strength development under lower temperature environment. In this paper, a novel approach to improve compressive strength of cement paste at low temperature by carbonation curing was put forwarded. The compressive strength of cement pastes under water-curing and CO2-cuirng at low temperature (5 °C) are both investigated. X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR) and Thermogravimetric analysis (TGA) were employed to analyze the phase changes in carbonated cement pastes. Scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDX) was adopted to examine the changes of morphologies and Mercury Intrusion Porosimeter (MIP) was used to analyze the pore structure of carbonated cement pastes. The results showed that the 1 d and 28 d compressive strength of carbonated samples was 18.2 % and 54.1 % higher than the values in hydrated samples at the corresponding ages. The 3 d compressive strength of carbonated sample was similar to the hydrated samples cured at 28 d. Calcium silicate hydrate (CSH), ettringite and portlandite (Ca(OH)2) were formed in hydrated sample, while calcium carbonate (CaCO3) and silica gel were generated in carbonated sample. The Ca(OH)2 was increased from 7.9 % (1 d) to 11.3 % (28 d) in hydrated samples, while the CaCO3 was increased from 20.9 % at 1 d to 37.7 % at 28 d in carbonated samples. The total porosity was reduced from 19.7 % in hydrated sample to 17.1 % in carbonated sample at 28 d. Furthermore, carbonation curing reduced the most probable pore diameters in comparison to hydrated samples. The needle-like ettringite was observed in hydrated sample, while typical prismatic calcite crystal was generated in carbonated samples. This paper confirmed that CO2 curing at low temperature could be an effective and promising way to obtain rapid compressive strength improvement.

Molecular characterization of accripin11, a soluble shell protein with an acidic C-terminus, identified in the prismatic layer of the Mediterranean fan mussel Pinna nobilis (Bivalvia, Pteriomorphia).

We have identified a novel shell protein, accripin11, as a major soluble component of the calcitic prisms of the fan mussel Pinna nobilis. Initially retrieved from a cDNA library, its full sequence is confirmed here by transcriptomic and proteomic approaches. The sequence of the mature protein is 103 residues with a theoretical molecular weight of 11 kDa and is moderately acidic (pI 6.74) except for its C-terminus which is highly enriched in aspartic acid. The protein exhibits a peculiar cysteine pattern in its central domain. The full sequence shares similarity with six other uncharacterized molluscan shell proteins from the orders Ostreida, Pteriida and Mytilida, all of which are pteriomorphids and produce a phylogenetically restricted pattern of nacro-prismatic shell microstructures. This suggests that accripin11 is a member of a family of clade-specific shell proteins. A 3D model of accripin11 was predicted with AlphaFold2, indicating that it possesses three short alpha helices and a disordered C-terminus. Recombinant accripin11 was tested in vitro for its ability to influence the crystallization of CaCO3 , while a polyclonal antibody was able to locate accripin11 to prismatic extracts, particularly in the acetic acid-soluble matrix. The putative functions of accripin11 are further discussed in relation to shell biomineralization.

Untangling the Mechanisms of Lattice Distortions in Biogenic Crystals across Scales.

Biomineralized structures are complex functional hierarchical assemblies composed of biomineral building blocks joined together by an organic phase. The formation of individual mineral units is governed by the cellular tissue component that orchestrates the process of biomineral nucleation, growth, and morphogenesis. These processes are imprinted in the structural, compositional, and crystallographic properties of the emerging biominerals on all scales. Measurement of these properties can provide crucial information on the mechanisms that are employed by the organism to form these complex 3D architectures and to unravel principles of their functionality. Nevertheless, so far, this has only been possible at the macroscopic scale, by averaging the properties of the entire composite assembly, or at the mesoscale, by looking at extremely small parts of the entire picture. In this study, the newly developed synchrotron-based dark-field X-ray microscopy method is employed to study the link between 3D crystallographic properties of relatively large calcitic prisms in the shell of the mollusc Pinna nobilis and their local lattice properties with extremely high angular resolution down to 0.001°. Mechanistic links between variations in local lattice parameters and spacing, crystal orientation, chemical composition, and the deposition process of the entire mineral unit are unraveled.

Investigating controls of shell growth features in a foundation bivalve species: seasonal trends and decadal changes in the California mussel

Abstract. Marine bivalve mollusk shells can offer valuable insights into past oceanographic variability and seasonality. Given its ecological and archeological significance, Mytilus californianus (California mussel) presents the opportunity to examine seasonal and decadal changes recorded in its shell over centuries to millennia. While dark–light growth bands in M. californianus shells could be advantageous for reconstructing past environments, uncertainties remain regarding shell structure, environmental controls of dark–light-band formation, and the amount of time represented by a dark–light pair. By analyzing a suite of M. californianus shells collected in 2002, 2003, 2019, and 2020 from Bodega Bay, California, we describe the mineralogical composition; establish relationships among the growth band pattern, micro-environment, and collection season; and compare shell structure and growth band expression between the archival (2002–2003) and modern (2019–2020) shells. We identified three mineralogical layers in M. californianus: an outer prismatic calcite layer, a middle aragonite layer, and a secondary inner prismatic calcite layer, which makes M. californianus the only Mytilus species to precipitate a secondary calcite layer. Within the inner calcite layer, light bands are strongly correlated with winter collection months and could be used to reconstruct periods with moderate, stable temperatures and minimal upwelling. Additionally, modern shells have significantly thinner inner calcite layers and more poorly expressed growth bands than the archival shells, although we also show that growth band contrast is strongly influenced by the micro-environment. Mytilus californianus from northern California is calcifying differently, and apparently more slowly, than it was 20 years ago.

Ribs of Pinna nobilis shell induce unexpected microstructural changes that provide unique mechanical properties

The reinforcement function of shell ribs depends not only on their vaulted morphology but also on their microstructure. They are part of the outer layer which, in the case of the Pinna nobilis bivalve, is built from almost monocrystalline calcitic prisms, always oriented perpendicular to the growth surfaces. Originally, prisms and their c-axes follow the radii of rib curvature, becoming oblique to the shell thickness direction. Later, prisms bend to reach the nacre layer perpendicularly, but their c-axes retain the initial orientation. Calcite grains form nonrandom boundaries. Most often, three twin disorientations arise, with two of them observed for the first time. Nano-indentation and impact tests demonstrate that the oblique orientation of c-axes significantly improves the hardness and fracture toughness of prisms. Moreover, compression tests reveal that the rib area achieves a unique strength of 700 MPa. The detection of the specific microstructure formed to toughen the shell is novel.

The influence of microbial mats on travertine precipitation in active hydrothermal systems (Central Italy)

AbstractThe study of hydrothermal travertines contributes to the understanding of the interaction between physico‐chemical processes and microbial mats in carbonate precipitation. Three active travertine sites were investigated in Central Italy to characterise the types of carbonate precipitates and the associated microbial mats at varying physico‐chemical parameters. Carbonate precipitated fabrics at the decimetre to millimetre‐scale and microbial mat composition vary with decreasing water temperature: (a) at relatively higher temperature (55–44°C) calcite and aragonite crystals precipitate on microbial mats of Chloroflexi and sulphur‐oxidizing microbes forming filamentous streamer fabrics with sparse cyanobacteria, (b) at intermediate temperature (44–40°C), rafts, coated gas bubbles and dendrites are associated with Spirulina cyanobacteria and other filamentous and rod‐shaped cyanobacteria, (c) low temperature (34–33°C) laminated crusts and oncoids forming in a terraced slope system are associated with diverse Oscillatoriales and Nostocales filamentous cyanobacteria, Spirulina and diatoms. At the microscale, carbonate precipitates are similar in the three sites consisting of prismatic calcite crystals organised in radial rosettes or fibrous aragonite spherulites (40–300 µm in diameter), overlying or embedded in Extracellular Polymeric Substances. Clotted peloidal micrite dominates at temperatures <40°C, also encrusting filamentous microbes. Carbonates are associated with gypsum crystals; extracellular polymeric substances are enriched in silicon, aluminium, magnesium, calcium, phosphorous and sulphur; authigenic aluminium‐silicates form aggregates on Extracellular Polymeric Substances. This study confirms that microbial communities in hydrothermal settings vary as a function of water temperature. Carbonate precipitates at the microscale are similar in the three settings, despite different microbial communities, suggesting that travertine precipitation, driven by carbon dioxide degassing, is influenced by biofilm extracellular polymeric substances acting as a substrate for crystal nucleation (Extracellular Polymeric Substances‐mediated mineralization) and affecting the resultant fabric types, independently from specific microbial community composition and metabolism.

Functional analyses of chitinolytic enzymes in the formation of calcite prisms in Pinctada fucata

The mollusk shells present distinctive microstructures that are formed by small amounts of organic matrices controlling the crystal growth of calcium carbonate. The shell of Pinctada fucata has the prismatic layer consisting of prisms of single calcite crystals and the nacreous layer consisting of aragonite tablets. The calcite crystal of prisms contains small angle grain boundaries caused by a dense intracrystalline organic matrix network to improve mechanical strength. Previously, we identified chitin and chitinolytic enzymes as components of this intracrystalline organic matrix. In this study, to reveal the function of those organic matrices in calcium carbonate crystallization, calcites synthesized in chitin gel with or without chitinolytic enzymes were analyzed by using transmission electron microscope (TEM) and atom probe tomography (APT), showing ion clusters derived from chitin inside of a calcite and small angle grain boundaries at optimal chitinolytic concentration. Furthermore, we performed the experiment in which chitinase inhibitor was injected into a living P. fucata. Nanoindentation and electron back scattered diffraction (EBSD) show that mechanical properties and crystal orientation were changed. These results suggested that chitinolytic enzymes work cooperatively with chitin to regulate the crystal growth and mechanical properties of the prismatic layer.

Mineralogy of volcanic calciocarbonatites from the Trig Point Hill debris flow, Kerimasi volcano, Tanzania: implications for the altered natrocarbonatite hypothesis

AbstractA major debris flow, the Trig Point Hill flow, originating from Kerimasi volcano (Tanzania) contains numerous blocks of extrusive/pyroclastic carbonatites similar to those exposed at the rim of the currently inactive crater. The blocks of calcite carbonatite consist of: (1) large clasts of corroded and altered coarse grained calcite; (2) primary prismatic inclusion bearing phenocrystal calcite; and (3) a matrix consisting primarily of fine-grained prismatic calcite. The large clasts are inclusion free and exhibit a ‘corduroy-like’ texture resulting from solution along cleavage planes. The resulting voids are filled by brown Fe–Mn hydroxides/oxides and secondary calcite. The prismatic or lath-shaped phenocrystal calcite is not altered and contains melt inclusions consisting principally of primary Na–Ca carbonates which contain earlier-formed crystals of monticellite, periclase, apatite, Mn–Mg-magnetite, Mn–Fe-sphalerite and Nb-perovskite. Individual Na–Ca carbonate inclusions are of uniform composition, and the overall range of all inclusions analysed (wt.%) is from 28.7 to 35.9 CaO; 16.7–23.6 Na2O; 0.5–2.8 K2O, with minor SO3(1.1–2.2) and SrO (0.34–1.0). The Na–Ca carbonate compositions are similar to that of shortite, although this phase is not present. The Na–Ca carbonates are considered to be primary deuteric phases and not secondary minerals formed after nyerereite. Monticellite shows limited compositional variation and contains 2–4 wt.% MnO and 12 wt.% FeO and is Mn-poor relative to monticellite in Oldoinyo Lengai natrocarbonatite. Periclase is Fe-bearing with up to 13 wt.% FeO. Spinels are Cr-free, Mn-poor and belong to the magnetite–magnesioferrite series in contrast to Mn-rich spinels of the magnetite–jacobsite series occurring in Oldoinyo Lengai natrocarbonatite. The matrix in which the ‘corduroy’ clasts and phenocrystal calcite are set consists of closely packed small prisms of calcite lacking melt inclusions, with interstitial fine-grained apatite, baryte, strontianite and minor fluorite. Pore spaces are filled with secondary Mn–Fe hydroxides/oxides, anhydrite and gypsum. The hypothesis that flow-aligned calcite in volcanic calciocarbonatites from Kerimasi, Tinderet, Homa and Catanda is altered nyerereite is discussed and it is considered that these calcite are either primary phases or altered melilite. The nyerereite alteration hypothesis is discussed with respect to the volumetric and compositional aspects of pseudomorphism by dissolution–precipitation replacement mechanisms. This study concludes that none of the volcanic calciocarbonatites containing flow-aligned calcite phenocrysts are altered natrocarbonatite.

Hard to Soft: Biogenic Absorbent Sponge-like Material from Waste Mussel Shells

Summary Mussel shells are a source of renewable CaCO3 and can be obtained from aquaculture waste streams. Valorization of waste shells relieves strain on landfills and aligns with the goals of a circular economy. Here, we present the preparation of an absorbent CaCO3 material, soft calcite (SC), prepared from waste blue mussel shells under mild conditions. Calcite is the only polymorph present in SC, despite the presence of aragonite in the shell. SC has a nest-like morphology, unlike the highly ordered calcite in the shell. SC is formed by the reassembly of calcite prisms and may be held together by the organic matrix “glue” from the original shell as evidenced by NMR spectroscopy. This inorganic sponge adsorbs dyes from aqueous solution and absorbs crude oil from seawater with good recyclability. Our results demonstrate how a natural structure can be modified in a sustainable fashion to yield a higher-value material.

Resolving Internal Structures and Composition of Biominerals: The Case of Calcitic Prisms of Mollusk Shells

Resolving Internal Structures and Composition of Biominerals: The Case of Calcitic Prisms of Mollusk Shells

Poorly crystallized hydroxyapatite and calcium silicate hydrate composites: Synthesis, characterization and soaking in simulated body fluid

Development of the composites based on substances with a high bioactivity potential is of current interest to medical materials science because composites' properties can be modified by varying the components ratios. Weakly crystallized calcium phosphates and calcium silicate hydrates, possessing higher chemical reactivity than their crystalline forms, are promising salts to be studied as biomaterials' constituents. In this study, precipitation from aqueous solutions was employed to obtain apatite and calcium silicate hydrate composites. Synthesized solids were examined without high-temperature thermal pretreatment using X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), laser diffraction, physical adsorption (BET method) and thermogravimetric analysis coupled with the mass spectrometry (TGA/MS). Compositions containing poorly crystallized carbonate-substituted hydroxyapatite, calcium silicate hydrate and calcite as an admixture were obtained by varying concentrations of the reagents. Soaking of the composite ceramics formed from freshly precipitated synthetic solids in simulated body fluid (SBF) at 37 °C for 14 days lead to formation of the surface layer of amorphous calcium phosphate. As the calcium silicate content in the composites increases, the coating's density and thickness also increase, because silicate ions act as active sites in the process of new phase nucleation. Furthermore, prismatic calcite crystals were identified to form on the lower side of ceramics. This may be caused by an increasing of local supersaturation with respect to calcium carbonate in small-volume confinement conditions during the experiment.