Using FlFFF and aTEM to determine trace metal–nanoparticle associations in riverbed sediment

K. L. Plathe; F. von der Kammer; M. Hassellöv; J. Moore; M. Murayama; T. Hofmann; M. F. Hochella

doi:10.1071/EN09111

RESEARCH ARTICLE

Using FlFFF and aTEM to determine trace metal–nanoparticle associations in riverbed sediment

K. L. Plathe ^A ^F , F. von der Kammer ^B , M. Hassellöv ^C , J. Moore ^D , M. Murayama ^E , T. Hofmann ^B and M. F. Hochella Jr. ^A

+ Author Affiliations

- Author Affiliations

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

^B Department for Environmental Geosciences, University of Vienna, Althanstraße 14 UZ AII, 1090 Vienna, Austria.

^C Department of Chemistry, University of Göteborg, SE-412 96, Göteborg, Sweden.

^D Department of Geology, University of Montana, 32 Campus Drive # 1296, Missoula, MT 59812, USA.

^E Institute for Critical Technology and Applied Science, Nanoscale Characterisation and Fabrication Laboratory, Virginia Tech, 1991 Kraft Drive, Blacksburg, VA 24061, USA.

^F Corresponding author. Email: plathekl@vt.edu

Environmental Chemistry 7(1) 82-93 https://doi.org/10.1071/EN09111
Submitted: 1 September 2009 Accepted: 22 December 2009 Published: 22 February 2010

Environmental context. Determining associations between trace metals and nanoparticles in contaminated systems is important in order to make decisions regarding remediation. This study analysed contaminated sediment from the Clark Fork River Superfund Site and discovered that in the <1-μm fraction the trace metals were almost exclusively associated with nanoparticulate Fe and Ti oxides. This information is relevant because nanoparticles are often more reactive and show altered properties compared with their bulk equivalents, therefore affecting metal toxicity and bioavailability.

Abstract. Analytical transmission electron microscopy (aTEM) and flow field flow fractionation (FlFFF) coupled to multi-angle laser light scattering (MALLS) and high-resolution inductively coupled plasma mass spectroscopy (HR-ICPMS) were utilised to elucidate relationships between trace metals and nanoparticles in contaminated sediment. Samples were obtained from the Clark Fork River (Montana, USA), where a large-scale dam removal project has released reservoir sediment contaminated with toxic trace metals (namely Pb, Zn, Cu and As) which had accumulated from a century of mining activities upstream. An aqueous extraction method was used to recover nanoparticles from the sediment for examination; FlFFF results indicate that the toxic metals are held in the nano-size fraction of the sediment and their peak shapes and size distributions correlate best with those for Fe and Ti. TEM data confirms this on a single nanoparticle scale; the toxic metals were found almost exclusively associated with nano-size oxide minerals, most commonly brookite, goethite and lepidocrocite.

Additional keywords: contaminated sediments, electron microscopy, field flow fractionation, ICPMS.

Acknowledgements

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. Special thanks go to Dr Heiko Langer at the University of Montana Geology Analytical Laboratory for measurement of the post-dam breach samples displayed in Fig. 1.

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