Molecular insights of oxidation process of iron nanoparticles: spectroscopic, magnetic, and microscopic evidence.

Oxidation behavior of nano-Fe(0) particles in an anoxic environment was determined using different state-of-the-art analytical approaches, including high resolution transmission electron microscopy (HR-TEM) combined with energy filtered transmission electron microscopy (EFTEM), X-ray absorption spectroscopy (XAS), and magnetic measurements. Oxidation in controlled experiments was compared in standard double distilled (DD) water, DD water spiked with trichloroethene (TCE), and TCE contaminated site water. Using HR-TEM and EFTEM, we observed a surface oxide layer (∼3 nm) formed immediately after the particles were exposed to water. XAS analysis followed the dynamic change in total metallic iron concentration and iron oxide concentration for the experimental duration of 35 days. The metallic iron concentration in nano-Fe(0) particles exposed to water, was ∼40% after 35 days; in contrast, the samples containing TCE were reduced to ∼15% and even to nil in the case of TCE contaminated site water, suggesting that the contaminants enhance the oxidation of nano-Fe(0). Frequency dependence measurements confirmed the formation of superparamagnetic particles in the system. Overall, our results suggest that nano-Fe(0) oxidized via the Fe(0) - Fe(OH)2 - Fe3O4 - (γ-Fe2O3) route and the formation of superparamagnetic maghemite nanoparticles due to disruption of the surface oxide layer.

Assessment of flushing methods for the removal of heavy chlorinated compounds DNAPL in an alluvial aquifer.

Immiscible mobilization and foam flushing were assessed as low surfactant consuming technologies, for the enhanced recovery of dense non-aqueous phase liquid (DNAPL) residual at a site contaminated by heavy chlorinated compounds. Preliminary experiments in well-controlled conditions demonstrated the phenomena involved in these remediation technologies and their limitations. Furthermore, we characterized the technologies according to by their surfactant consumption (per kg of DNAPL recovered) and the final DNAPL saturation reached. Surfactant foam flushing (SFF) produced lower DNAPL saturation than immiscible mobilization, thanks to its higher viscosity. However, its efficiency is strongly correlated to the pressure gradient (▽P) used during injection, and that is limited by risks of soil fracturing. The two technologies were tested in field cells (10m×10m×10m) delimited by cement/bentonite walls anchored in the clayey substratum. The deepest soil layer was the most contaminated. It was composed of silt-sandy soil and had an average hydraulic conductivity of 10-4ms-1. Field results show that we should now model flushing fluid propagation to design efficient set-ups for recovering the displaced DNAPL.

Assessment of potential positive effects of nZVI surface modification and concentration levels on TCE dechlorination in the presence of competing strong oxidants, using an experimental design.

Nanoscale zero-valent iron (nZVI) particles are efficient for the remediation of aquifers polluted by trichloroethylene (TCE). But for on-site applications, their reactivity can be affected by the presence of common inorganic co-pollutants, which are equally reduced by nZVI particles. The aim of this study was to assess the potential positive effects of nZVI surface modification and concentration level on TCE removal in the concomitant presence of two strong oxidants, i.e., Cr(VI) and NO3(-). A design of experiments, testing four factors (i.e. nZVI concentration, nZVI surface modification, Cr(VI) concentration and NO3(-) concentration), was used to select the best trials for the identification of the main effects of the factors and of the factors interactions. The effects of these factors were studied by measuring the following responses: TCE removal rates at different times, degradation kinetic rates, and the transformation products formed. As expected, TCE degradation was delayed or inhibited in most of the experiments, due to the presence of inorganics. The negative effects of co-pollutants can be palliated by combining surface modification with a slight increase in nZVI concentration. Encouragingly, complete TCE removal was achieved for some given experimental conditions. Noteworthily, nZVI surface modification was found to promote the efficient degradation of TCE. When degradation occurred, TCE was mainly transformed into innocuous non-chlorinated transformation products, while hazardous chlorinated transformation products accounted for a small percentage of the mass-balance.