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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.

Engineered nanomaterials (ENMs) are used to enhance the properties of many manufactured products and technologies. Increased use of ENMs will inevitably lead to their release into the environment. An important route of exposure is through the waste stream, where ENMs will enter wastewater treatment plants (WWTPs), undergo transformations, and be discharged with treated effluent or biosolids. To better understand the fate of a common ENM in WWTPs, experiments with laboratory-scale activated sludge reactors and pristine and citrate-functionalized CeO2 nanoparticles (NPs) were conducted. Greater than 90% of the CeO2 introduced was observed to associate with biosolids. This association was accompanied by reduction of the Ce(IV) NPs to Ce(III). After 5 weeks in the reactor, 44 ± 4% reduction was observed for the pristine NPs and 31 ± 3% for the citrate-functionalized NPs, illustrating surface functionality dependence. Thermodynamic arguments suggest that the likely Ce(III) phase generated would be Ce2S3. This study indicates that the majority of CeO2 NPs (>90% by mass) entering WWTPs will be associated with the solid phase, and a significant portion will be present as Ce(III). At maximum, 10% of the CeO2 will remain in the effluent and be discharged as a Ce(IV) phase, governed by cerianite (CeO2).

Although several laboratory studies showed that Mn-oxides are capable of oxidizing Cr(II) to Cr(VI), very few have reported evidence for such a reaction in natural systems. This study presents new evidence for this redox reaction between Cr(III) and Mn-oxides in a lateritic regolith developed on ultramafic rocks in New Caledonia. The studied lateritic regolith presents several units with contrasting amounts of major (Fe, Al, Si, and Mg) and trace (Mn, Cr, Ni, Co) elements, which are related to varying mineralogical compositions. Bulk XANES analyses show the occurrence of Cr(VI) (up to 20 wt % of total chromium) in the unit of the regolith which is also enriched in Mn (up to 21.7 wt % MnO), whereas almost no Cr(VI) is detected elsewhere. X-ray powder diffraction indicates that the large amounts of Mn in this unit of the regolith are due to the occurrence of Mn-oxides (identified as a mixture of asbolane, lithiophorite and birnessite) and Mn K-edge XANES data indicate that Mn occurs mainly as Mn(IV) in this unit, although small amounts of Mn(III) could also be detected. These results strongly suggest a direct role of the Mn-oxides on the occurrence of Cr(VI) through a redox reaction between Cr(III) and Mn(IV) and/or Mn(III). Owing to the much larger toxicity and solubility of Cr(VI), such a co-occurrence of Cr and Mn-oxides in these soils could then represent an important risk for the environment. However, the significant amounts of Cr(VI) released after reacting the samples from the studied sequence with a 0.1 M (NH)4H2PO4 solution, designed to remove tightly sorbed chromate species, suggest that Cr(VI) mainly occurs as sorption complexes. This hypothesis is reinforced by spatially resolved XANES analyses, which show that Cr(VI) is associated with both Mn- and Fe-oxides, and especially at the boundary between these two mineral species. Such a distribution of Cr(VI) suggests a possible readsorption of Cr(VI) onto surrounding Fe-oxyhydroxides (mainly goethite) after oxidation by the Mn(IV)-oxides. These results, added to leaching tests with a 0.01 M CaCl2 solution indicative of low exchangeability of Cr in the investigated samples, suggest that secondary sorption reactions onto Fe-oxides might significantly decrease the environmental impact of the oxidation of Cr(III) to Cr(VI) by Mn-oxides.

Although the current production of oxide nanoparticles may be modest, the wide range of proposed applications and forecasted growth in production has raised questions about the potential impact of these nanoparticles on the environment and human health. Iron oxide nanoparticles have been proposed for an increasing number of biomedical applications although in vitro toxicity depending on the particles coating has been evidenced. The aim of this study was to examine the potential in vitro cyto- and genotoxicity on human dermal fibroblasts of DMSA-coated maghemite nanoparticles (NmDMSA) as a function of well-defined physicochemical states. Well-stabilized NmDMSA produced weak cytotoxic and no genotoxic effects. This is attributed in part to the DMSA coating, which serves as a barrier for a direct contact between nano-oxide and fibroblasts, inhibiting a potential toxic effect.