International audienceThe molecular environment of iodine in reference inorganic and organic compounds, and in dry humic and fulvic acids (HAs and FAs) extracted from subsurface and deep aquifers was probed by iodine L 3-edge X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) of iodine spectra from HAs and FAs resembled those of organic references and displayed structural features consistent with iodine forming covalent bonds with organic molecules. Simulation of XANES spectra by linear combination of reference spectra suggested the predominance of iodine forming covalent bonds to aromatic rings (aromatic-bound iodine). Comparison of extended X-ray absorption fine structure (EXAFS) spectra of reference and samples further showed that iodine was surrounded by carbon shells at distances comparables to those for references containing aromatic-bound iodine. Quantitative analysis of EXAFS spectra indicated that iodine was bound to about one carbon at a distance d (I–C) of 2.01(4)–2.04(9) A ˚ , which was comparable to the distances observed for aromatic-bound iodine in references (1.99(1)–2.07(6) A ˚), and significantly shorter than that observed for aliphatic-bound iodine (2.15(2)–2.16(2) A ˚). These results are in agreement with previous conclusions from X-ray photoelectron spectros-copy and from electrospray ionization mass spectrometry. These results collectively suggest that the aromatic-bound iodine is stable in the various aquifers of this study

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The iodination of Gorleben and synthetic humic substances (HS) was studied complementarily by UV-visible and X-ray Photoelectron Spectroscopy (XPS). The I2(aq) consumption kinetics could neither be linearly correlated to [H+] nor to HS concentration as already observed in the literature. Nevertheless, the electrophilic substitution mechanism was further evidenced by the production of both I3- and I-, leading to a covalent bonding. The XPS analysis of the iodinated samples confirmed the covalent bonding between iodine and carbon of HS for all the samples

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During XPS analysis, the soft X-ray-induced reduction of metals such as Cr(VI) and Ce(IV) in oxides has been reported in the literature and some mechanisms have been proposed to explain this phenomenon. The reduction of U(VI) by the beam during X-ray Photoelectron Spectroscopy has been already reported in the literature but only for U(VI) sorbed or precipitated onto solids with reducing properties (as micas or pyrites) for whose Fe(II) can also induce the reduction of U(VI), or onto TiO2 whose the photocatalytic properties are well known. The objective of this paper is to investigate the effects of X-ray beam on U(VI) bulk compounds (UO3, UO2(OH)2, (UO2)2SiO4, UO2(CH3COO)2 and UO2C2O4). Successive U4f, U5f, C1s XPS spectra were recorded and compared as a function of the irradiation time. The XPS photoreduction of U(VI) into U(IV) is only observed for uranyl compounds containing organic matter (uranyl acetate and uranyl oxalate). Considering the evolution of the C1s signal during the X-ray irradiation, a significant decrease of the C O component simultaneously to the U(VI) reduction is observed, which suggests a desorption of CO or other volatile organic products from the solid surface. All these results on U(VI) bulk compounds indicate the important role of organic carbon species in the photoreduction process and to explain these observations, a photoreduction mechanism has been suggested

The electrical properties of the corrosion layers on archaeological iron artefacts were determined by Conductive Atomic Force Microscopy. Different corrosion products were studied: Fe II carbonates, magnetite entrapped in the carbonate, and iron sulfides. The results indicate that the ferrous carbonate matrix is insulating, and that magnetite and iron sulfides have a conductive character, although these phases are not systematically connected to the metal. This suggests that electrons produced by the anodic dissolution of metal would be conducted to the external part of the corrosion product layer through a three-dimensional network of connected magnetite strips passing through the ferrous carbonate matrix.

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