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Study on nanophase iron oxyhydroxides in freshwater ferromanganese nodules from Green Bay, Lake Michigan, with implications for the adsorption of As and heavy metals

  • Seungyeol Lee , Zhizhang Shen and Huifang Xu EMAIL logo
Published/Copyright: September 1, 2016
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American Mineralogist
From the journal American Mineralogist Volume 101 Issue 9

Abstract

Nanophase Fe-oxyhydroxides in freshwater ferromanganese nodules (FFN) from Green Bay, Lake Michigan, and adsorbed arsenate have been investigated by X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Z-contrast imaging, and ab initio calculations using the density functional theory (DFT). The samples from northern Green Bay can be divided into two types: Fe-Mn nodules and Fe-rich nodules. The manganese-bearing phases are todorokite, birnessite, and buserite. The iron-bearing phases are feroxyhyte, nanophase goethite, two-line ferrihydrite, and nanophase FeOOH with guyanaite structure. Z-contrast images of the Fe-oxyhydroxides show ordered FeOOH nano-domains with guyanaite structure intergrown with nanophase goethite. The FeOOH nanophase is a precursor to the goethite. Henceforth, we will refer to it as “proto-goethite.” DFT calculations indicate that goethite is more stable than proto-goethite. Our results suggest that ordering between Fe and vacancies in octahedral sites result in the transformation from feroxyhyte to goethite through a proto-goethite intermediate phase. Combining Z-contrast images and TEM-EDS reveals that arsenate (AsO43−) tetrahedra are preferentially adsorbed on the proto-goethite (001) surface via tridentate adsorption. Our study directly shows the atomic positions of Fe-oxyhydroxides with associated trace elements. The methods can be applied for identifying structures of nano-phases and adsorbed trace elements and heavy metals.

Keywords: XRD; HRTEM; Z-contrast imaging; ab initio; two-line ferrihydrite; proto-goethite; nanophase goethite; feroxyhyte; ferromanganese nodule; arsenic

Special collection papers can be found online at http://www.minsocam.org/MSA/AmMin/special-collections.html.

Acknowledgments

The authors acknowledge the financial support from NASA Astrobiology Institute (N07-5489). The authors thank Carl Bowser for providing the samples and their locations, Hiromi Konishi for assistance in acquiring Z-contrast images, Izabela Szlufarska for allowing us to access computing facility, Gabor J. Kemeny of Middleton Spectral Vision and Michael Beauchaine of Bruker AXS for XRF mapping. The authors also thank Philip E. Brown, John W. Valley, Clark M. Johnson, Eric E. Roden, and Franklin Hobbs for their helpful suggestions.

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Received: 2016-2-19
Accepted: 2016-4-21
Published Online: 2016-9-1
Published in Print: 2016-9-1

© 2016 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2016-5729
Keywords for this article
XRD; HRTEM; Z-contrast imaging; ab initio; two-line ferrihydrite; proto-goethite; nanophase goethite; feroxyhyte; ferromanganese nodule; arsenic

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Styles of aqueous alteration on Mars
  3. Highlights and Breakthroughs
  4. Study on nanophase iron oxyhydroxides in freshwater ferromanganese nodules from Green Bay, Lake Michigan
  5. Review
  6. Redox variations in the inner solar system with new constraints from vanadium XANES in spinels
  7. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  8. From bone to fossil: A review of the diagenesis of bioapatite
  9. Special Collection: Olivine
  10. Nickel–cobalt contents of olivine record origins of mantle peridotite and related rocks
  11. Special Collection: Rates And Depths Of Magma Ascent On Earth
  12. Experimental simulation of bubble nucleation and magma ascent in basaltic systems: Implications for Stromboli volcano
  13. Special Collection: Nanominerals and Mineral Nanoparticles
  14. Study on nanophase iron oxyhydroxides in freshwater ferromanganese nodules from Green Bay, Lake Michigan, with implications for the adsorption of As and heavy metals
  15. Special Collection: Building Planets: The Dynamics and Geochemistry of Core Formation
  16. The effects of shear deformation on planetesimal core segregation: Results from in-situ X-ray micro-tomography
  17. Special Collection: Martian Rocks and Minerals: Perspectives from Rovers, Orbiters, and Meteorites
  18. VNIR multispectral observations of aqueous alteration materials by the Pancams on the Spirit and Opportunity Mars Exploration Rovers
  19. Research Article
  20. Experimental investigation of the kinetics of the spinel-to-garnet transformation in peridotite: A preliminary study
  21. Research Article
  22. Thermodynamics, self-diffusion, and structure of liquid NaAlSi3O8 to 30 GPa by classical molecular dynamics simulations
  23. Research Article
  24. Magnetite plaquettes are naturally asymmetric materials in meteorites
  25. Research Article
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