Engineered TiO2 nanoparticles (TiO2-NPs) are present in a large variety of consumer products, and are produced in largest amount. The building industry is a major sector using TiO2-NPs, especially in paints. The fate of NPs after their release in the environment is still largely unknown, and their possible transfer in plants and subsequent impacts have not been studied in detail. The foliar transfer pathway is even less understood than the root pathway. In this study, lettuces were exposed to pristine TiO2-NPs and aged paint leachate containing TiO2-NPs and microparticles (TiO2-MPs). Internalization and in situ speciation of Ti were investigated by a combination of microscopic and spectroscopic techniques. Not only TiO2-NPs pristine and from aged paints, but also TiO2-MPs were internalized in lettuce leaves, and observed in all types of tissues. No change in speciation was noticed, but an organic coating of TiO2-NPs is likely. Phytotoxicity markers were tested for plants exposed to pristine TiO2-NPs. No acute phytotoxicity was observed; variations were only observed in glutathione and phytochelatin levels but remained low as compared to typical values. These results obtained on the foliar uptake mechanisms of nano- and microparticles are important in the perspective of risk assessment of atmospheric contaminations.
International audienceX-ray absorption spectroscopy at the Mg K-edge is used to obtain information on magnesium environment in minerals, silicate and alumino-silicate glasses. First-principles XANES calculations are performed for minerals using a plane-wave density functional formalism with core-hole effects treated in a supercell approach. The good agreement obtained between experimental and theoretical spectra provides useful information to interpret the spectral features. With the help of calculation, the position of the first peak of XANES spectra is related to both coordination and polyhedron distortion changes. In alumino-silicate glasses, magnesium is found to be mainly 5-fold coordinated to oxygen whatever the aluminum saturation index value. In silicate glasses, magnesium coordination increases from 4 in Cs-, Rb- and K-bearing glasses to 5 in Na- and Li-bearing glasses but remains equal as the polymerization degree of the glass varies. The variation of the C feature (position and intensity) is strongly related to the alkali type providing information on the medium range order
International audienceThe Cerro del Almirez massif (Spain) represents a unique fragment of serpentinized oceanic lithosphere that has been first equilibrated in the antigorite stability field (Atg-serpentinites) and then dehydrated into chlorite–olivine–orthopyroxene (Chl-harzburgites) at eclogite facies conditions during subduction. The massif preserves a dehydration front between Atg-serpentinites and Chl-harzburgites. It constitutes a suitable place to study redox changes in serpentinites and the nature of the released fluids during their dehydration. Relative to abyssal serpentinites, Atg-serpentinites display a low Fe3+/FeTotal(BR) (=0.55) and magnetite modal content (=2.8–4.3 wt%). Micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy measurements of serpentines at the Fe–K edge show that antigorite has a lower Fe3+/FeTotal ratio (=0.48) than oceanic lizardite/chrysotile assemblages. The onset of Atg-serpentinites dehydration is marked by the crystallization of a Fe3+-rich antigorite (Fe3+/FeTotal = 0.6–0.75) in equilibrium with secondary olivine and by a decrease in magnetite amount (=1.6–2.2 wt%). This suggests a preferential partitioning of Fe3+ into serpentine rather than into olivine. The Atg-breakdown is marked by a decrease in Fe3+/FeTotal(BR) (=0.34–0.41), the crystallization of Fe2+-rich phases and the quasi-disappearance of magnetite (=0.6–1.4 wt.%). The observation of Fe3+-rich hematite and ilmenite intergrowths suggests that the O2 released by the crystallization of Fe2+-rich phases could promote hematite crystallization and a subsequent increase in fo2 inside the portion of the subducted mantle. Serpentinite dehydration could thus produce highly oxidized fluids in subduction zones and contribute to the oxidization of the sub-arc mantle wedge
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