Calcium carbonate (CaCO3) is abundant on Earth, is a major component of marine biominerals and thus of sedimentary and metamorphic rocks and it plays a major role in the global carbon cycle by storing atmospheric CO2into solid biominerals. Six crystalline polymorphs of CaCO3are known—3 anhydrous: calcite, aragonite, vaterite, and 3 hydrated: ikaite (CaCO3·6H2O), monohydrocalcite (CaCO3·1H2O, MHC), and calcium carbonate hemihydrate (CaCO3·½H2O, CCHH). CCHH was recently discovered and characterized, but exclusively as a synthetic material, not as a naturally occurring mineral. Here, analyzing 200 million spectra with Myriad Mapping (MM) of nanoscale mineral phases, we find CCHH and MHC, along with amorphous precursors, on freshly deposited coral skeleton and nacre surfaces, but not on sea urchin spines. Thus, biomineralization pathways are more complex and diverse than previously understood, opening new questions on isotopes and climate. Crystalline precursors are more accessible than amorphous ones to other spectroscopies and diffraction, in natural and bio-inspired materials.
Assessment of Optimal Conditions for Marine Invertebrate Cell-Mediated Mineralization of Organic Matrices
Cellular strategies and regulation of their crystallization mechanisms are essential to the formation of biominerals, and harnessing these strategies will be important for the future creation of novel non-native biominerals that recapitulate the impressive properties biominerals possess. Harnessing these biosynthetic strategies requires an understanding of the interplay between insoluble organic matrices, mineral precursors, and soluble organic and inorganic additives. Our long-range goal is to use a sea anemone model system (Nematostella vectensis) to examine the role of intrinsically disordered proteins (IDPs) found in native biomineral systems. Here, we study how ambient temperatures (25–37 °C) and seawater solution compositions (varying NaCl and Mg ratios) will affect the infiltration of organic matrices with calcium carbonate mineral precursors generated through a polymer-induced liquid-precursor (PILP) process. Fibrillar collagen matrices were used to assess whether solution conditions were suitable for intrafibrillar mineralization, and SEM with EDS was used to analyze mineral infiltration. Conditions of temperatures 30 °C and above and with low Mg:Ca ratios were determined to be suitable conditions for calcium carbonate infiltration. The information obtained from these observations may be useful for the manipulation and study of cellular secreted IDPs in our quest to create novel biosynthetic materials.
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- Award ID(s):
- 1755364
- NSF-PAR ID:
- 10405684
- Date Published:
- Journal Name:
- Biomimetics
- Volume:
- 7
- Issue:
- 3
- ISSN:
- 2313-7673
- Page Range / eLocation ID:
- 86
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
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Abstract Biominerals are organic–mineral composites formed by living organisms. They are the hardest and toughest tissues in those organisms, are often polycrystalline, and their mesostructure (which includes nano‐ and microscale crystallite size, shape, arrangement, and orientation) can vary dramatically. Marine biominerals may be aragonite, vaterite, or calcite, all calcium carbonate (CaCO3) polymorphs, differing in crystal structure. Unexpectedly, diverse CaCO3biominerals such as coral skeletons and nacre share a similar characteristic: Adjacent crystals are slightly misoriented. This observation is documented quantitatively at the micro‐ and nanoscales, using polarization‐dependent imaging contrast mapping (PIC mapping), and the slight misorientations are consistently between 1° and 40°. Nanoindentation shows that both polycrystalline biominerals and abiotic synthetic spherulites are tougher than single‐crystalline geologic aragonite. Molecular dynamics (MD) simulations of bicrystals at the molecular scale reveal that aragonite, vaterite, and calcite exhibit toughness maxima when the bicrystals are misoriented by 10°, 20°, and 30°, respectively, demonstrating that slight misorientation alone can increase fracture toughness. Slight‐misorientation‐toughening can be harnessed for synthesis of bioinspired materials that only require one material, are not limited to specific top‐down architecture, and are easily achieved by self‐assembly of organic molecules (e.g., aspirin, chocolate), polymers, metals, and ceramics well beyond biominerals.
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After a wildfire event, ash is a newly formed surficial soil layer with microscale properties such as roughness, morphology, and chemical composition that may impact how ashes form fabrics in situ and so affect the overall hydrological conditions of a burned area (infiltration capacity, permeability, etc.). To examine the effects of ash microscale properties on macroscale behavior, eight wildfire ash samples from California were characterized physically (specific gravity, specific surface area, particle size, etc.), chemically (elemental composition, organic and inorganic carbon content, etc.), and geotechnically (strength, compaction, saturated hydraulic conductivity, etc.). The tested ashes were found to contain predominantly organic unburned carbons and carbonates derived from the combustion of calcium-oxalate rich fuels in temperatures likely ranging from 300°C to 500°C. Ashes had high specific surface areas because morphologically, particles had highly texturized and porous surfaces. Additional water was necessary to coat the particle surfaces, which led to high liquid limits and compaction optimum moisture contents. Hydraulic conductivity values were within range for silty sands (10^−5–10^−3 cm/s), and specimens had friction angles near 30°. However, tested ashes consistently demonstrated high void ratios and low bulk densities during testing for strength, hydraulic conductivity, and compaction. These anomalies were attributed to unusual carbonate morphologies; the high interparticle friction of these phases allowed ashes to form looser fabrics than a typical silty sand and contributed to the measured high void ratios, low maximum dry unit weights, and high friction angles. Overall, we hypothesize that the relative amounts of inorganic versus organic constituents in our wildfire ash samples affected how the ashes formed fabrics and so affected their geotechnical properties.more » « less
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Microbially induced calcite precipitation (MICP) or biocementation is a bio-mediated process that can be used to improve the engineering properties of granular soils through calcium carbonate precipitation. Although most commonly this process is accomplished using microbial urea hydrolysis, other microbial metabolic pathways can be used to enable biocementation with the potential to eliminate ammonium byproducts. Microbial organic acid oxidation presents one alternative pathway by which increases in solution carbonate species can be generated to enable calcium carbonate mineral formation. While past studies have considered the potential of this microbial pathway to enable biocementation for surficial applications, to date few studies have examined the feasibility of this pathway for subsurface applications wherein dissolved oxygen is more limited. In this study, 18 small-scale batch experiments were performed to investigate the ability of microbial organic acid oxidation to enable biocementation soil improvement. Experiments investigated the feasibility of using both acetate and citrate oxidation to mediate biocementation as well as the effect of differences in techniques used to supply dissolved oxygen, the effect of supplied growth factors, bicarbonate salt additions, and solution sampling frequency. Results suggest that aerobic oxidation of acetate and citrate can be used to enable calcium carbonate biocementation, though ensuring dissolved oxygen availability appears to be critical towards enabling this process.more » « less
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null (Ed.)Living systems have not only the exemplary capability to fabricate materials (e.g., wood, bone) under ambient conditions but they also consist of living cells that imbue them with properties like growth and self-regeneration. Like a seed that can grow into a sturdy living wood, can living cells alone serve as the primary building block to fabricate stiff materials? Here is reported the fabrication of stiff living materials (SLMs) produced entirely from microbial cells, without the incorporation of any structural biopolymers (e.g., cellulose, chitin, collagen) or biominerals (e.g., hydroxyapatite, calcium carbonate) that are known to impart stiffness to biological materials. Remarkably, SLMs are also lightweight, strong, and resistant to organic solvents and can self- regenerate. This living materials technology can serve as a powerful biomanu- facturing platform to design and develop advanced structural and cellular materials in a sustainable manner.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/biomimetics7030086
