Feature Papers in Biomineralization and Biominerals

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Biomineralization and Biominerals".

Deadline for manuscript submissions: closed (31 December 2023) | Viewed by 15059

Special Issue Editors

National d'Histoire Naturelle, Biodiversité, 75005 Paris, France
Interests: biomineralization; mollusc shells; coral skeletons; bone and teeth; mineralogy; organic matrices; SEM; AFM; chromatography; electrophoresis; Infrared and Raman spectroscopy; XANES; electron microprobe; fossilization and diagenesis
Special Issues, Collections and Topics in MDPI journals
EaSTCHEM, School of Chemistry, University of Edinburgh, David Brewster Road, Edinburgh EH9 3FJ, UK
Interests: biogenic minerals; organic-inorganic hybrid materials; protein-crystal interactions; (cryo)electron microscopy; soft matter
Special Issues, Collections and Topics in MDPI journals
Museum National d’Histoire Naturelle, CR2P, 8 rue Buffon, 75005 Paris, France
Interests: coral and shell growth-modes at the micrometer and infra-micrometer levels; microstructure and fossilization: fossils as environmental archives; microstructural development of the pearl layers: from early post-grafting stages to nacre biomineralization
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Biomineralization is the process leading to the formation of biominerals by organisms. Thus, the structure and composition of such biominerals are dependant upon the producing organisms. This Special Issue will contain invitation-only original research and  review articles from prominent researchers in the field, covering a range of topics from the structure to the composition of mineral and organic components of plants, fungi, algae, vertebrates and invertebrates. Methods for characterizing biominerals at the macro, micro, nano and atomic levels are included. Contributions from researchers working on fundamental research and/or applications in biology, medicine, inspired biomaterials, evolution, diagenesis, (palaeo)environmental reconstructions, (palaeo)biodiversity, etc., based on modern and ancient (fossil) biominerals, are welcome.

Dr. Yannicke Dauphin
Dr. Fabio Nudelman
Dr. Jean-Pierre Cuif
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • shells
  • tests
  • bone
  • teeth
  • micro–nanostructure
  • phase transformation
  • mineralogy
  • crystallography
  • composition
  • organic components

Published Papers (9 papers)

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Research

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14 pages, 19461 KiB  
Article
The Caudofoveata (Mollusca) Spicule as a Biomineralization Model: Unique Features Revealed by Combined Microscopy Methods
by Camila Wendt, André L. Rossi, Jefferson Cypriano, Cleo Dilnei de Castro Oliveira, Corinne Arrouvel, Jacques Werckmann and Marcos Farina
Minerals 2023, 13(6), 750; https://doi.org/10.3390/min13060750 - 31 May 2023
Viewed by 1168
Abstract
Caudofoveates are benthic organisms that reside in the deep waters of continental slopes in the world. They are considered to be a group that is of phylogenetic and ecological importance for the phylum Mollusca. However, they remain poorly studied. In this work, we [...] Read more.
Caudofoveates are benthic organisms that reside in the deep waters of continental slopes in the world. They are considered to be a group that is of phylogenetic and ecological importance for the phylum Mollusca. However, they remain poorly studied. In this work, we revealed the structure of the spicules of Caudofoveatan mollusks Falcidens sp. The spicules presented a hierarchical organization pattern across different length scales. Various imaging and analytical methods related to light and electron microscopy were employed to characterize the samples. The primary imaging methods utilized included: low voltage field emission scanning electron microscopy (FEG-SEM), focused ion beam-scanning electron microscopy (FIB-SEM), high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and electron diffraction. In addition, we performed a physicochemical analysis by electron energy loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDS). A crucial factor for successfully obtaining the results was the preparation of lamellae from the spicules without damaging the original structures, achieved using FIB-SEM. This allowed us to obtain diffraction patterns of significant areas of well-preserved sections (lamellae) of the spicules in specific directions and demonstrate for the first time that the bulk of these structures is organized as a single crystal of calcium carbonate aragonite. On the other hand, AFM imaging of the spicules’ dorsal surface revealed a wavy appearance, composed of myriads of small, pointed crystallites oriented along the spicules’ longer axis (i.e., the c-axis of the aragonite). The organization pattern of these small crystallites, the possible presence of twins, the relationship between confinement conditions and accessory ions in the preference for mineral polymorphs, and the single crystalline appearance of the entire spicule, along with the observation of growth lines, provide support for further studies employing Caudofoveata spicules as a model for biomineralization studies. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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14 pages, 2634 KiB  
Article
Towards the Chemical Analysis of Diatoms’ Silicon Storage Pools: A Differential Centrifugation-Based Separation Approach
by Tobias Reichelt, Tobias Bode, Paul-Felix Jordan and Eike Brunner
Minerals 2023, 13(5), 653; https://doi.org/10.3390/min13050653 - 09 May 2023
Cited by 1 | Viewed by 1359
Abstract
Diatoms are unicellular algae and occur ubiquitously in almost every marine and freshwater habitat on earth. They produce intricately structured cell walls, which mainly consist of amorphous silica. To synthesize their cell walls, diatoms take up monosilicic acid from the environment and store [...] Read more.
Diatoms are unicellular algae and occur ubiquitously in almost every marine and freshwater habitat on earth. They produce intricately structured cell walls, which mainly consist of amorphous silica. To synthesize their cell walls, diatoms take up monosilicic acid from the environment and store it. These silicon storage pools (SSPs) can exceed the solubility of silicic acid by one to two orders of magnitude, as observed in various diatom species. However, their chemical composition and cellular localization has not yet been elucidated. It is suggested that SSPs may consist of stabilized aggregates such as pre-condensed silica particles or silica-containing vesicles. Isolation protocols for SSPs without significant chemical modification are required to prove such hypotheses. A critical issue is the efficient separation of components of the SSPs from cell wall fragments or artefacts, which may interfere with analytical methods targeting silicon. To this end, a comparative study was performed on exponentially grown cells and extracted, purified cell walls (biosilica) to observe the sedimentation behavior after lysis. Cell cultures were lysed by bead beating and then fractionated by differential centrifugation. The obtained fractions were analyzed for total silicon content (tSi) using molybdenum blue assay (MBA) after alkaline treatment. It was revealed that cell wall fragments are almost absent in fractions above 1000 × g. Compared with biosilica, a significantly higher silicon concentration is found in lysed cell pellets after centrifugation at moderately high forces. The differences correspond to a few percent of total cellular silicon, which are assumed to be part of SSPs. Only relatively low amounts of silica/silicic acid remain in the supernatant at high centrifugal forces. This indicates that SSPs are mainly present in larger aggregates that sediment at lower centrifugal forces. According to Stokes’ law, only silica particles below ca. 25 nm radius would remain in the final supernatant. This leads to the conclusion that SSPs must mainly consist of larger silica particles and/or are associated with larger compartments/aggregates. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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19 pages, 5878 KiB  
Article
Integrated Information on the Structure and Composition of the Ostrich Eggshell (Struthio camelus)
by Alberto Pérez-Huerta, Jean-Philip Brugal, Murielle Salomé, Clemens N. Z. Schmitt and Yannicke Dauphin
Minerals 2023, 13(4), 481; https://doi.org/10.3390/min13040481 - 29 Mar 2023
Viewed by 1672
Abstract
Ostrich eggshells are excellent examples of avian biomineralization. Interest in these eggshells is focused on their potential as a food source, example of a biomaterial for medical and industrial applications, and the use of fossil remains for paleoenvironmental reconstructions. Due to this interest, [...] Read more.
Ostrich eggshells are excellent examples of avian biomineralization. Interest in these eggshells is focused on their potential as a food source, example of a biomaterial for medical and industrial applications, and the use of fossil remains for paleoenvironmental reconstructions. Due to this interest, there is some information about aspects of eggshell biomineralization, but it is scattered in different publications and is limited in scope about mineralogy-crystallography and/or composition. Here, we re-examine the biomineralization of the Struthio eggshells focusing on the structure, from macro- to nano-scales, crystallography, and composition of mineral and organic phases. Our results show that there is a very tight biomineralization control, from well-defined structures at nanoscale to precise crystallographic orientation of calcite crystals, in the formation of a biomineral that is unparalleled in other avian eggshells. Overall, this finding would explain the thickness and excellent mechanical properties of ostrich eggshells. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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16 pages, 6165 KiB  
Article
Deciphering Alterations of Rodent Bones through In Vitro Digestion: An Avenue to Understand Pre-Diagenetic Agents?
by Christiane Denys, Denné N. Reed and Yannicke Dauphin
Minerals 2023, 13(1), 124; https://doi.org/10.3390/min13010124 - 14 Jan 2023
Viewed by 1436
Abstract
Recent taphonomic studies have shown that avian predators such as owls are responsible for most small-mammal fossil accumulations, and that predators cause bone loss and breakage as well as modification to the surface of bones that are preserved. However, the specific physiochemical alterations [...] Read more.
Recent taphonomic studies have shown that avian predators such as owls are responsible for most small-mammal fossil accumulations, and that predators cause bone loss and breakage as well as modification to the surface of bones that are preserved. However, the specific physiochemical alterations and the alterations of bone microstructures that predators induce remain poorly understood. In order to better separate and characterize the effects of bone digestion by owls, we performed an experimental study to simulate digestion by a predator. We put fresh rodent long bones into various solutions to simulate the digestive effects of predators. We first tested an acid solution, followed by other solutions containing key enzymes such as trypsin, lipase, and trypsin + lipase. Next, we compared the results of the simulated digestion experiments with partly digested long bones recovered from Tyto alba and Bubo bubo pellets. We observed that acid action alone did not reproduce the modifications observed on bones from owl pellets, while the enzymatic activity (notably trypsin and trypsin + lipase) produced modifications most similar to those observed on the bones from the owl pellets. These results open a promising field of future experimentation to better understand the early diagenetic modification induced in small mammal bones by digestion, which can improve our ability to recognize the role of nocturnal predators in fossil accumulations. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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16 pages, 6221 KiB  
Article
Mud Crab’s Mottled, Deep-Blue Exoskeleton: Surface Morphology and Internal Microstructure
by Tadanobu Inoue, Erina Kitahara, Yuka Hara and Koji Nakazato
Minerals 2022, 12(12), 1607; https://doi.org/10.3390/min12121607 - 14 Dec 2022
Cited by 1 | Viewed by 1356
Abstract
The claws of the mud crab, Scylla serrata, are huge in comparison with its body size. Many bulges ranging from 5 to 23 μm in height and 90 to 146 µm in diameter were observed on the mottled, deep-blue exoskeleton surface of [...] Read more.
The claws of the mud crab, Scylla serrata, are huge in comparison with its body size. Many bulges ranging from 5 to 23 μm in height and 90 to 146 µm in diameter were observed on the mottled, deep-blue exoskeleton surface of the mud crab’s claw. These cuticle bulges were closely related to irregularly present exocuticles on the surface layer of the exoskeleton’s cross section. The bulges exist between the exocuticles, and at the apex of these bulges was a tube that bundled many pore canals that penetrated the exoskeleton. This tube was thick (62–66 µm) near the inner side and narrowed (12–22 µm) toward the outer surface. On the other hand, the exocuticles had a heterogeneous tissue structure in a coarse region extending normally to the surface, with a diameter of 3 to 7 µm, and a dense region between them. Calcium concentrations were high in the dense region, and phosphorus and magnesium concentrations were high in the coarse region. As a result, the mechanical properties (hardness: H and modulus: Er) were distributed inside the exocuticle, and the mapping of H and Er using a nanoindentation test clarified the heterogeneity. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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21 pages, 2409 KiB  
Article
Morpho-Constitutional Classification of Urinary Stones as Prospective Approach for the Management of Human Pathological Biomineralization: New Insights from Southern Italy
by Francesco Izzo, Alessio Langella, Chiara Germinario, Celestino Grifa, Ettore Varricchio, Maria Chiara Di Meo, Luigi Salzano, Giuseppe Lotrecchiano and Mariano Mercurio
Minerals 2022, 12(11), 1421; https://doi.org/10.3390/min12111421 - 09 Nov 2022
Cited by 3 | Viewed by 3518
Abstract
The present investigation exposes the main results raised from an active collaboration started in 2018 with the San Pio Hospital (Benevento, Southern Italy), aiming at a detailed mineralogical investigation of urinary stones of patients from the Campania region. Forty-nine uroliths (both bladder and [...] Read more.
The present investigation exposes the main results raised from an active collaboration started in 2018 with the San Pio Hospital (Benevento, Southern Italy), aiming at a detailed mineralogical investigation of urinary stones of patients from the Campania region. Forty-nine uroliths (both bladder and kidney stones) have been surgically collected from patients admitted between 2018 and 2020 at the Department of Urology of the San Pio Hospital and characterized for clinical purposes and environmental biomonitoring from a mineralogical point of view. Possible causes and environmental implications were inferred according to the morpho-constitutional classification of the uroliths carried out by means of a conventional analytical approach. The mineralogical frequency distribution of uroliths from the Campanian region can be discussed as a function of dietary, socio-demographic, and environmental risk factors. Whewellite [CaC2O4·H2O] and weddellite [CaC2O4·(2+x)H2O], along with anhydrous calcium oxalate, represent the main mineralogical phases forming the biominerals examined here. Worth to note is that the percentage of oxalates in the Campanian region (ca. 51%) is quite comparable to those of other Mediterranean areas. Frequent uricite [C5H4N4O3] (ca. 33%), mainly observed in bladder stones of older male patients, could be related to an incorrect lifestyle and dietary habits. Occurrence of lower percentages of phosphate (i.e., brushite [CaHPO4·2(H2O)] and carbonated apatite [Ca10(PO4CO3)6(OH)8]) and mixed stones (such as, for example, a mixture of ammonium urate [NH4C5H3N4O3] and calcium oxalates) indicates specific etiopathogenetic mechanisms, suggesting proper therapeutical approaches. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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17 pages, 1162 KiB  
Article
Oxygen Isotopes in Carbonate and Phosphate of Modern Mammal Bioapatite: New Data and Critical Revision after about 25 Years from the First Recognitions
by Paola Iacumin, Mattia Rossi, Enricomaria Selmo and Giampiero Venturelli
Minerals 2022, 12(10), 1204; https://doi.org/10.3390/min12101204 - 24 Sep 2022
Viewed by 1217
Abstract
Oxygen and carbon isotopes of well-preserved skeletal remains give relevant support to archaeological and environmental reconstructions. However, the preservation of the skeletal remains must be preliminarily checked. About twenty-five years ago, a diagnostic method based on the oxygen isotope ratio in the phosphate, [...] Read more.
Oxygen and carbon isotopes of well-preserved skeletal remains give relevant support to archaeological and environmental reconstructions. However, the preservation of the skeletal remains must be preliminarily checked. About twenty-five years ago, a diagnostic method based on the oxygen isotope ratio in the phosphate, δ(O18/O16)Ph, and carbonate, δ(O18/O16)Carb, of bioapatite of modern mammals was proposed: for well-preserved samples, the δ(O18/O16)Ph and δ(O18/O16)Carb should plot near the regression line δ(O18/O16)Ph on δ(O18/O16)Carb obtained for modern mammals. In the last twenty years, techniques of analysis have changed. In the past, BiPO4 or Ag3PO4 were precipitated from dissolved bioapatite and analysed with the fluorination technique, whereas at present, temperature reduction (HTR) in a glassy carbon reactor with CO release is commonly used. Taking into account the HTR technique, for some modern mammals, we report a new δ(O18/O16)Ph + 1 on  δ(O18/O16)Carb + 1 regression line, and related dispersion of the data that, in addition to mineralogical and structural methods, may be used to select samples reliable for archaeological use. In the past, other similar regression lines on modern mammals were defined by several authors. However, statistical results indicate that data used for these regression lines cannot be pooled because the hypothesis of a similar elevation is rejected. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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Review

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14 pages, 3575 KiB  
Review
Formation of the Outer Shell Layer in Pinctada margaritifera: Structural and Biochemical Evidence for a Sequential Development of the Calcite Units
by Jean-Pierre Cuif, Angélique Fougerouse, Cedrik Lo and Yannicke Dauphin
Minerals 2023, 13(10), 1301; https://doi.org/10.3390/min13101301 - 08 Oct 2023
Cited by 1 | Viewed by 785
Abstract
Calcite prismatic units that form the outer layers of “nacro-prismatic” Pelecypod shells are often used as biomineralization models due to their individual size, simple shape, and spatial arrangement. However, these models do not take into account the developmental history of the shell. After [...] Read more.
Calcite prismatic units that form the outer layers of “nacro-prismatic” Pelecypod shells are often used as biomineralization models due to their individual size, simple shape, and spatial arrangement. However, these models do not take into account the developmental history of the shell. After metamorphosis, a series of structural changes predating production of the prisms is commonly missing. Consequently, this study focuses on the early stages of the calcite biomineralization area of the Pinctada margaritifera as it occurs in the outer mantle groove. It also includes the structural changes following the typical “simple prism” status. The interpretation takes advantage of an ancient result from genomic investigations: the localisation of Prisilkin-39, a protein associated with production of the calcite units. A revision of the initial interpretation concerning the position of this Prisilkin-39-producing area provides additional evidence of the role of two distinct mineralizing sectors in the formation of the calcite units in the Pinctada shell: the outer mantle groove and the anterior mineralizing area of the shell mantle. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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13 pages, 5459 KiB  
Review
Phosphatic Biomineralization in Scyphozoa (Cnidaria): A Review
by Olev Vinn
Minerals 2022, 12(10), 1316; https://doi.org/10.3390/min12101316 - 18 Oct 2022
Cited by 8 | Viewed by 1581
Abstract
Phosphatic biomineralization is unknown in modern species of Scyphozoa (Cnidaria). However, some extinct groups of Scyphozoa, such as conulariids and Sphenothallus, were capable of secreting phosphatic exoskeletons. Both conulariids and Sphenothallus used apatite to improve the mechanical properties of their skeletons, which [...] Read more.
Phosphatic biomineralization is unknown in modern species of Scyphozoa (Cnidaria). However, some extinct groups of Scyphozoa, such as conulariids and Sphenothallus, were capable of secreting phosphatic exoskeletons. Both conulariids and Sphenothallus used apatite to improve the mechanical properties of their skeletons, which offered better protection than the non-biomineralized periderms. The skeletons of conulariids and Sphenothallus have a lamellar microstructure. The shell lamellae of conulariids are often pierced by tiny pores. Several apatitic mineral structures have been described in conulariids and Sphenothallus, including plywood-like structures. Different lattice parameters of the apatite indicate that the biomineralization mechanisms of the phosphatic cnidarians Sphenothallus and conulariids differed from each other. Full article
(This article belongs to the Special Issue Feature Papers in Biomineralization and Biominerals)
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