Supplementary Materials for

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1 advances.sciencemag.org/cgi/content/full/3/3/e /dc1 Supplementary Materials for Biomimetic mineral self-organization from silica-rich spring waters Juan Manuel García-Ruiz, Elias Nakouzi, Electra Kotopoulou, Leonardo Tamborrino, Oliver Steinbock The PDF file includes: Published 17 March 2017, Sci. Adv. 3, e (2017) DOI: /sciadv 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 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 Other Supplementary Material for this manuscript includes the following: (available at advances.sciencemag.org/cgi/content/full/3/3/e /dc1) 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 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.

2 table S1. Comparative chemical analysis of the Ney water by Feth et al. (17), Barnes et al. (18), and this study. Elemental concentrations are in ppm, conductivity is in µs/cm. Reference Feth et al., 1961 *a/b Barnes et al., 1972 This study ph 11.6/ conductivity alkalinity (tot as CaCO3) T C 12.2/ SiO2 3970/ Ba B + 242/ Ca / <0.4 Mg / Na / K + 135/ S 295/ Fe Cl / SO / CO / HCO <5

3 fig. S1. Sampling and geological setting of the Ney spring. (A) Simplified geological map of the Ney Springs area (modified from 35). Geological formation acronyms and description: OUM, Ordovician Trinity Ultramafic Sheet; OGB, Ordovician Gabbro and diorite (hornblende gabbro hornblende diorite - quartz diorite); DC, Early Devonian Compley Greenstone (andesitic and basaltic volcanic breccia, tuff, pillow lavas); DK, Early-Middle Devonian Kennett Fm. (interbedded dark siliceous shale, rhyolitic tuff and limestone); MB, Mississippian Bragford Fm. (interbedded dark shale, siltstone, sandstone and locally abundant pebble-conglomerate); JGR, Jurassic granitoid plutons (quartz diorite to granite composition); TVS, Eocene-Oligocene volcanic and sedimentary rocks (andesitic and basaltic flows, breccia,

4 tuff, minor rhyolitic tuff and intercalated sedimentary units); QV, Quaternary volcanic rocks (Basaltic and andesitic flows and pyroclastic rocks); QG, Quaternary glacial deposits (glacial debris). (B) Ruins of the main fountain of Aqua de Ney spa. (C) Hexagonal concrete well, next to the Ney Creek, where the alkaline water was collected. (D) Comparison of the ph values and the silica concentration (ppm) needed for the synthesis of biomorphs and MSH membranes with the ones of the Ney natural spring waters.

5 fig. S2. Electron micrographs of barium-based self-assembled structures. (A, B) Smoothly curved shapes, (C, D) biomorphs with distinct topographic ridges, and (E, F) elongated globules. High-resolution images of (G) nanoparticle and (H) nanowire assemblies. Scale bars: (A, B) 50 µm, (C, E) 20 µm, (D, F) 10 µm (G, H) 200 nm.

6 fig. S3. Electron micrographs of calcium-based structures grown at ph (A, B) Calcite mesocrystals. (C, D) Nanocrystalline structure of spherical assemblies. (E-J) Platelet texture in calcite mesocrystals. Scale bars: (A,B) 20 µm; (C) 2 µm; (D,H,I,J) 200 nm; (E,F) 500 nm; (G) 5 µm.

7 fig. S4. XRD pattern and infrared spectrum of the calcium-based structures. (A) Powder XRD of calcium carbonate based structures showing calcite (filled, blue circles) and vaterite (open, red circles) phases. (B) IR spectrum showing the characteristic peaks for silica (grey squares) and calcium carbonate (black circles).

8 fig. S5. MSH tubular membrane produced by reaction of the Co salt (CoCl2 6H2O) pellet with the Ney water. (A) Fluid jetting after the formation of the membrane at time t1. (B) Tubular structure obtained at time t2=t1+3min. (C) Growth of the tube and continuous fluid jetting at time t3=t1+6min. (D) Growth of the tube at time t4=t1+14min. (E) Complete development of the tubular structure at time t5=t1+52min.

9 fig. S6. MSH tubular membrane produced by the reaction of the Fe(II) salt pellet (FeCl2 4H2O) with the Ney water. (A) Formation of the membrane at time t1. (B) Tubular structure obtained at time t2=t1+30min. (C) Growth of the tube and continuous fluid jetting at time t3=t1+35min. (D) Growth of the tube at time t4=t1+44min. (E) Complete development of the tubular structure at time t5=t1+183min.

10 fig. S7. Chromatograms indicating the production of CO2(g) upon reaction of the pellets with the Ney water. (A) Upon reaction with the Fe (II) pellet. (B) The Zn (II) pellet. (C) The Cu (II) pellet. (D) Chromatogram of blank sample (only the Ney water). Note that the CO2 is obtained from the HCO3 - and CO3 2- species as the ph of the solution decreases.

11 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 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.