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The amorphous Zn biomineralization at Naracauli stream, Sardinia: electron microscopy and X-ray absorption spectroscopy

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Abstract

An amorphous Zn biomineralization (“white mud”), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.

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Acknowledgments

This research was carried out under the European project UMBRELLA (FP7-ENV-2008-1 no. 226870). Additional support was provided by MIUR PRIN 2010–2011 funds to P.L. One anonymous reviewer is greatly appreciated for his suggestions and criticism.

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Authors and Affiliations

  1. Department of Chemical and Geological Sciences, University of Cagliari, 09127, Cagliari, Italy

    D. Medas, P. Lattanzi, F. Podda & G. De Giudici

  2. Physics Department, University of Roma Tre, Rome, Italy

    C. Meneghini

  3. CNR-IOM-OGG c/o ESRF, 6 rue Jules Horowitz, 38043, Grenoble, France

    A. Trapananti

  4. Environmental Characterization, Prevention and Recovery Unit, ENEA-Casaccia, Rome, Italy

    A. Sprocati

  5. National Research Council, Institute of Translational Pharmacology, UOS of Cagliari, Scientific and Technological Park of Sardinia POLARIS, Pula, Italy

    M. A. Casu

  6. Sardegna Ricerche/CRS4–Telemicroscopy Lab, Scientific and Technological Park of Sardinia POLARIS, Pula, Italy

    E. Musu

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  1. D. Medas
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  2. P. Lattanzi
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  3. F. Podda
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  7. M. A. Casu
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  8. E. Musu
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  9. G. De Giudici
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Correspondence to D. Medas.

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Responsible editor: Stuart Simpson

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Fig. S1

a) X-ray diffraction patterns of natural samples WM4, WM5, WM15, and WM20 collected along the Naracauli stream ph = phyllosilicates, qz = quartz. b) Synchrotron XRD pattern collected with E = 18.0597 keV (λ = 0.6865 Å): ticks signal the quartz phase, the arrows point out reflections of unknown phase (a phyllosilicate?). (PDF 142 kb)

Fig. S2

Plots showing a) Zn vs Si concentration, b) Zn vs Cd concentration, and c) Zn vs Pb concentration in “white mud” samples. (PDF 125 kb)

Fig. S3

Scanning Electron Microscopy (SEM) images (secondary electrons, SE). a) Micrometric sheaths making up the Zn biomineralization. b) and c) Images showing the presence of isolated tubules of hydrozincite (indicated by dashed rectangles) in the amorphous biomineralization (indicated by arrows). d) EDS elemental spectra showing the chemical composition of the hydrozincite sheaths. Notice the marked decrease of the Si signal (probably referable to quartz and/or diatoms) with respect to spectrum in Fig. S2d. (PDF 207 kb)

Fig. S4

a) Experimental data (points) and best fits curves (full lines) for references compounds, vertically shifted for sake of clarity. b) Moduli of the Fourier transforms of experimental EXAFS spectra (points) and best fit (full lines). (PDF 180 kb)

Table S1

Fit parameters for EXAFS analysis of the reference compounds. The number in brackets indicates the uncertainty on the last digit of the refined parameters. CN = coordination number; R = interatomic distance; σ2 = Debye-Waller factor; R 2 = best fit factor; ΔE = edge energy shift. CN* were kept fixed to the theoretical value. σ2* for the Zn-Si shell of willemite was constrained to the same value as in the Zn-Zn shell. (PDF 133 kb)

Table S2

Fit parameters for EXAFS analysis of the biomineral samples. The number in brackets indicates the uncertainty on the last digit of the refined parameters. CN = coordination number; R = interatomic distance; σ2 = Debye-Waller; R 2 = best fit factor; ΔE = edge energy shift. CN* for the first shells were kept fixed to 4. σ2* for the second Zn-Zn shells (*) were constrained to the same value as in hemimorphite. (PDF 169 kb)

Table S3

Range of values of pH, total dissolved solids (TDS), alkalinity (HCO3 -), Si, Zn, Cd, Pb and Zn2+/CO3 2- molar ratio in waters collected at the hydrozincite station (hdz), and amorphous phase station (WM): minimum (Min), maximum (Max), mean (X) and standard deviation (σ). N indicates the number of samples. (PDF 106 kb)

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Medas, D., Lattanzi, P., Podda, F. et al. The amorphous Zn biomineralization at Naracauli stream, Sardinia: electron microscopy and X-ray absorption spectroscopy. Environ Sci Pollut Res 21, 6775–6782 (2014). https://doi.org/10.1007/s11356-013-1886-4

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