Nanoparticle - Heavy Metal Associations in Riverbed Sediments
Plathe, Kelly Lee
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Relationships between trace metals and nanoparticles were investigated using analytical transmission electron microscopy (aTEM) and asymmetric flow field flow fractionation (aFlFFF) coupled to both multi-angle laser light scattering (MALLS) and high resolution-inductively coupled plasma mass spectroscopy (HR-ICPMS). Riverbed sediment samples were taken from the Clark Fork River in 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 accumulated from one and a half centuries of mining activities upstream. An aqueous extraction method was used to attempt to separate the nanoparticles from the bulk sediment. After analysis of initial results, it was found that low density clays were being selected for in this process and made up a major portion of the particles within the extracts. However, it was also realized that the metals of interest were associated almost exclusively with nano-sized Fe and Ti oxides. In order to more fully examine these relationships, a density separation method, using sodium polytungstate (2.8g/cm3), was developed to separate these higher density oxides from the lower density clays. The heavy fraction was then subjected to an aqueous extraction routine to extract the nanoparticulate fraction. FFF results indicated a smaller size distribution and more ideal fractionation with this method. The aFlFFF-HR-ICPMS profiles for Fe and Ti also matched strongly with the data for the trace metals. The majority of particles analyzed with the TEM were nano-sized Fe and Ti oxides (most commonly goethite, ferrihydrite and brookite), which typically had trace metals associated with them. In many cases, it was aggregates of these nano oxides that were found hosting trace metals. Nanoparticles and aggregates are known to behave differently than their bulk mineral phases or constituent particles, respectively. Nanoparticles are also capable of extended transport in the environment. For these reasons, it is important that their associations with toxic trace metals be extensively evaluated, as they will affect the bioavailability and toxicity of these metals with implications for any type of contaminant sediment relocation, dam removal or metal contaminated site.
- Doctoral Dissertations