Research ArticleGEOLOGY

Biomimetic mineral self-organization from silica-rich spring waters

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Science Advances  17 Mar 2017:
Vol. 3, no. 3, e1602285
DOI: 10.1126/sciadv.1602285
  • Fig. 1 Barium carbonate–based structures grown using the Ney water.

    Smoothly curved biomorphic shapes (A and B), helical structures (C and D), and flat sheets (E) showing oscillatory features (F). (G and I) Higher-resolution images reveal the nanocrystals that constitute the biomorphs. (H) Nanocrystal alignment direction obtained from the correlation analyses of the micrograph in (G); inset shows a representative correlation map. (J and K) Some of the structures consist of nanowires. (L) Infrared spectrum shows silica (gray squares) and crystalline barium carbonate (black circles) peaks. (M) X-ray diffraction (XRD) diffractogram with the characteristic witherite peaks. a.u., arbitrary units. Scale bars, 50 μm (A), 200 μm (B), 10 μm (C), 2 μm (D), 20 μm (E and F), 1 μm (G and J), and 200 nm (I and K).

  • Fig. 2 Calcium carbonate–based structures.

    (A to D) Morphological trend from classical rhombohedra to nanostructured aggregates with increasing pH. (E to G) Scanning electron microscopy (SEM) image (F) of a crystal aggregate showing two distinctive morphologies and the Raman spectrum of the calcitic (E) and vateritic (G) domains of the crystal aggregate. (H and K) Hierarchical structures of stacked nanoplatelets consisting of nanoparticles. Scale bars, 20 μm (A and C), 5 μm (B, D, and F), 2 μm (H and I), 500 nm (J), and 50 nm (K).

  • Fig. 3 Silica gardens.

    (A to C) MSH tubular membranes produced by reaction of the Co salt pellet with the Ney water. (D) Comparative histogram of the chemical composition [energy-dispersive x-ray spectroscopy (EDX)] of the inner part (gray) and the outer part (black) of the Co-based tube. (E) Raman spectra of the Co-based tubes produced in Ney water (black) and laboratory sodium silicate (Sod. Sil.) solutions (gray). (F to H) MSH tubular membrane produced by the reaction of the Fe(II) salt pellet with the Ney water. (I) Comparative histogram for the chemical composition (EDX) of the inner part (gray) and the outer part (black) of the Fe-based tube. (J) Raman spectra of the Fe-based tubes produced in Ney water (black curve) and laboratory sodium silicate solutions (gray curve).

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/3/e1602285/DC1

    table S1. Comparative chemical analysis of the Ney water by Feth et al. (17), Barnes et al. (18), and this study.

    fig. S1. Sampling and geological setting of the Ney spring.

    fig. S2. Electron micrographs of barium-based self-assembled structures.

    fig. S3. Electron micrographs of calcium-based structures grown at pH 10.5.

    fig. S4. XRD pattern and infrared spectrum of the calcium-based structures.

    fig. S5. MSH tubular membrane produced by reaction of the Co salt (CoCl2•6H2O) pellet with the Ney water.

    fig. S6. MSH tubular membrane produced by the reaction of the Fe(II) salt pellet (FeCl2•4H2O) with the Ney water.

    fig. S7. Chromatograms indicating the production of CO2(g) upon reaction of the pellets with the Ney water.

    movie S1. The alkaline Ney spring showing the hexagonal fabric of the well and the circular hole for feet treatment that were in use during the working time of the Aqua de Ney Spa, inactive since 1941.

    movie S2. CO2 bubbling and bursting of reaction products of the Fe2(SO4)3•9H2O pellet and the sodium silicate solution.

    movie S3. CO2 bubbling and bursting of reaction products of the CuCl2•2H2O pellet and the sodium silicate solution.

    movie S4. CO2 bubbling and bursting of reaction products of the ZnCl2 pellet and the sodium silicate solution.

  • Supplementary Materials

    This PDF file includes:

    • table S1. Comparative chemical analysis of the Ney water by Feth et al. (17), Barnes et al. (18), and this study.
    • fig. S1. Sampling and geological setting of the Ney spring.
    • fig. S2. Electron micrographs of barium-based self-assembled structures.
    • fig. S3. Electron micrographs of calcium-based structures grown at pH 10.5.
    • fig. S4. XRD pattern and infrared spectrum of the calcium-based structures.
    • fig. S5. MSH tubular membrane produced by reaction of the Co salt (CoCl2•6H2O) pellet with the Ney water.
    • fig. S6. MSH tubular membrane produced by the reaction of the Fe(II) salt pellet (FeCl2•4H2O) with the Ney water.
    • fig. S7. Chromatograms indicating the production of CO2(g) upon reaction of the pellets with the Ney water.
    • Legends for movies S1 to S4

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    Other Supplementary Material for this manuscript includes the following:

    • movie S1 (.mp4 format). The alkaline Ney spring showing the hexagonal fabric of the well and the circular hole for feet treatment that were in use during the working time of the Aqua de Ney Spa, inactive since 1941.
    • movie S2 (.mp4 format). CO2 bubbling and bursting of reaction products of the Fe2(SO4)3•9H2O pellet and the sodium silicate solution.
    • movie S3 (.mp4 format). CO2 bubbling and bursting of reaction products of the CuCl2•2H2O pellet and the sodium silicate solution.
    • movie S4 (.mp4 format). CO2 bubbling and bursting of reaction products of the ZnCl2 pellet and the sodium silicate solution.

    Files in this Data Supplement:

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