The influence of surface-bound Fe(II) on uranium oxidation state and speciation was studied as a function of time (6 min-72 h) and pH (6.1-8.5) in a U(VI)-Fe(II)-montmorillonite (Ca-montmorillonite, MONT) system under CO(2)-free, anoxic (O(2) <1 ppmv) conditions. The results show a rapid removal of U(VI) from the aqueous solution within 1 h under all pH conditions. U L(III)-edge X-ray absorption near-edge structure spectroscopy shows that 96% of the total sorbed U(VI) is reduced at pH 8.5. However, the extent of reduction significantly decreases at lower pH values as specifically sorbed Fe(II) concentration decreases. The reduction kinetics followed by X-ray photoelectron spectroscopy during 24 h at pH 7.5 demonstrates the presence of partially reduced surface species containing U(VI) and U(IV). Thermodynamically predicted mixed valence solids like U(3)O(8)/beta-U(3)O(7)/U(4)O(9) do not precipitate as verified by transmission electron microscopy and extended X-ray absorption fine-structure spectroscopy. This is also supported by the bicarbonate extraction results. The measured redox potentials of Fe(II)/Fe(III)-MONT suspensions are controlled by the Fe(II)/hydrous ferric oxide [HFO(s)] couple at pH 6.2 and by the Fe(II)/lepidocrocite [gamma-FeOOH(s)] couple at pH 7.5. The key finding of our study is the formation of a sorbed molecular form of U(IV) in abiotic reduction of U(VI) by sorbed Fe(II) at the surface of montmorillonite.

Electron transfer at the mineral/water interface: Selenium reduction by ferrous iron sorbed on clay. Geochimica et Cosmochimica Acta, Elsevier, 2007, 71 (23) , selenite was sorbed as outer-sphere sorption complex, covering only part of the positive edge sites, as verified by a structure-based MUSIC model and Se K-edge XAS (X-ray absorption spectroscopy). When selenite was added to montmorillonite previously equilibrated with Fe 2+ solution however, slow reduction of Se and formation of a solid phase was observed with Se K-edge XANES (x-ray absorption near-edge spectroscopy) and EXAFS (extended x-ray absorption finestructure) spectroscopy. Iterative transformation factor analysis of XANES and EXAFS spectra suggested that only one Se reaction product formed, which was identified as nano-particulate Se(0). Even after one month, only 75% of the initially sorbed Se(IV) was reduced to this solid species. Mössbauer spectrometry revealed that before and after addition and reduction of Se, 5% of total sorbed Fe occurred as

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A range of talc-like phyllosilicates were prepared via a hydrothermal synthesis performed at five different temperatures from 160 to 350 C. The organization of the lattice and the degree of crystallinity of the new materials were evaluated by different techniques such as XRD, FTIR, solid-state 29 Si NMR, TEM, FEG-SEM and TG-DTA. When synthesized at low temperature the material presents high degree of hydration, low crystallinity and flawed structure. This was attributed to stevensite-talc interstratified product present in the samples. The stevensite/talc ratio and the hydration decrease in the talc-like phyllosilicate samples when the hydrothermal synthesis temperature increases and so the crystallinity becomes higher. A thermal treatment at 500 C allowed a significant flaw reduction in talclike phyllosilicate structure; the synthesized sample at 350 C and heat treated presents a structure close to that of talc. The different talc-like phyllosilicates were grafted covalently by two organoalkoxysilane reagents, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole (IM2H) and 2-hydroxy-4-(3triethoxysilylpropoxy)-diphenylketone (HTDK). The grafted amounts of the hybrids, determined by elemental analysis and confirmed by thermogravimetric data, are dependent on the hydrothermal synthesis temperature and organoalkoxysilanes; they become smaller when the synthesis temperature increases and when HTDK is used. FTIR and solid-state 13 C CP MAS NMR were applied to characterize the grafted organic groups. So, in this work it is shown that by choosing the hydrothermal synthesis temperature or by performing an additional annealing it is possible to adjust the amount of defects in the structure of talc-like phyllosilicates which seems to be strongly correlated to the grafting performance.

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