Molecular Insights of Oxidation Process of Iron Nanoparticles: Spectroscopic, Magnetic, and Microscopic Evidence

• Published in: Environmental science & technology 2014-12, Vol.48 (23), p.13888-13894
• Main Authors: Kumar, Naresh, Auffan, Mélanie, Gattacceca, Jérôme, Rose, Jérôme, Olivi, Luca, Borschneck, Daniel, Kvapil, Petr, Jublot, Michael, Kaifas, Delphine, Malleret, Laure, Doumenq, Pierre, Bottero, Jean-Yves
• Format: Article
• Language: English
• Subjects: Applied sciences; Contamination; Earth sciences; Earth, ocean, space; Electrons; Engineering and environment geology. Geothermics; Environmental Sciences; Exact sciences and technology; Ferric Compounds - chemistry; Groundwaters; Iron; Iron - chemistry; Magnetics; Metal Nanoparticles - chemistry; Microscopy, Electron, Transmission; Nanoparticles; Nanotechnology - methods; Natural water pollution; Oxidation; Oxidation-Reduction; Oxides - chemistry; Pollution; Pollution, environment geology; Transmission electron microscopy; Trichloroethylene - chemistry; Water Pollutants, Chemical - chemistry; Water treatment and pollution; X-Ray Absorption Spectroscopy; X-Ray Diffraction
• ISSN: 0013-936X; 1520-5851
• DOI: 10.1021/es503154q

Oxidation behavior of nano-Fe0 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-Fe0 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-Fe0. Frequency dependence measurements confirmed the formation of superparamagnetic particles in the system. Overall, our results suggest that nano-Fe0 oxidized via the Fe0 – Fe­(OH)2 – Fe3O4 – (γ-Fe2O3) route and the formation of superparamagnetic maghemite nanoparticles due to disruption of the surface oxide layer.