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The structure and transformation of the nanomineral schwertmannite: a synthetic analog representative of field samples

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Abstract

The phase transformation of schwertmannite, an iron oxyhydroxide sulfate nanomineral synthesized at room temperature and at 75 °C using H2O2 to drive the precipitation of schwertmannite from ferrous sulfate (Regenspurg et al. in Geochim Cosmochim Acta 68:1185–1197, 2004), was studied using high-resolution transmission electron microscopy. The results of this study suggest that schwertmannite synthesized using this method should not be described as a single phase with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers in diameter, within a characteristic ‘pin-cushion’-like amorphous matrix. The difference in synthesis temperature affected the density of the needles on the schwertmannite surface. The needles on the higher-temperature schwertmannite displayed a dendritic morphology, whereas the needles on the room-temperature schwertmannite were more closely packed. Visible lattice fringes in the schwertmannite samples are consistent with the powder X-ray diffraction (XRD) pattern taken on the bulk schwertmannite and also matched d-spacings for goethite, indicating a close structural relationship between schwertmannite and goethite. The incomplete transformation from schwertmannite to goethite over 24 h at 75 °C was tracked using XRD and TEM. TEM images suggest that the sample collected after 24 h consists of aggregates of goethite nanocrystals. Comparing the synthetic schwertmannite in this study to a study on schwertmannite produced at 85 °C, which used ferric sulfate, reveals that synthesis conditions can result in significant differences in needle crystal structure. The bulk powder XRD patterns for the schwertmannite produced using these two samples were indistinguishable from one another. Future studies using synthetic schwertmannite should account for these differences when determining schwertmannite’s structure, reactivity, and capacity to take up elements like arsenic. The schwertmannite synthesized by the Regenspurg et al. method produces a mineral that is consistent with the structure and morphology of natural schwertmannite observed in our previous study using XRD and TEM, making this an ideal synthetic method for laboratory-based mineralogical and geochemical studies that intend to be environmentally relevant.

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Acknowledgments

We thank the ICTAS Nanocharacterization and Fabrication Laboratory (NCFL) at Virginia Tech and the Materials Science and Engineering Nanoscale Materials Characterization Facility (MSE-NMCF) at the University of Virginia for the use of their Titan microscopes. Grants from the US Department of Energy (DE-FG02-06ER15786) and the Institute for Critical Technology and Applied Sciences at Virginia Tech provided major financial support for this project. We are also appreciative of the support from the National Science Foundation (NSF) and the Environmental Protection Agency through the Center for Environmental Implications of NanoTechnology (CEINT) funded under NSF Cooperative Agreement EF-0830093. Fellowship support for this research was provided by the National Science Foundation (NSF IGERT grant DGE-0504196). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of NSF, EPA, or DOE.

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Authors and Affiliations

  1. Environmental Nanoscience and Technology Laboratory, ICTAS, Virginia Tech, Blacksburg, VA, 24061, USA

    Rebecca A. French & Michael F. Hochella Jr.

  2. Department of Geosciences, Virginia Tech, 4044 Derring Hall, Blacksburg, VA, 24061, USA

    Rebecca A. French & Michael F. Hochella Jr.

  3. Department of Materials Science, Virginia Tech, Blacksburg, VA, 24061, USA

    Niven Monsegue & Mitsuhiro Murayama

  4. Nanoscale Characterization and Fabrication Laboratory, ICTAS, Virginia Tech, Blacksburg, VA, 24061, USA

    Mitsuhiro Murayama

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  1. Rebecca A. French
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  2. Niven Monsegue
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  4. Michael F. Hochella Jr.
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Correspondence to Rebecca A. French.

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French, R.A., Monsegue, N., Murayama, M. et al. The structure and transformation of the nanomineral schwertmannite: a synthetic analog representative of field samples. Phys Chem Minerals 41, 237–246 (2014). https://doi.org/10.1007/s00269-013-0641-1

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