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.

Summary The long‐term effects of intermittent flooding on soil properties were studied in field experiments on a Vertisol cropped with rice in Senegal. The dominant clay minerals were smectite and kaolinite. When the soil was reduced after flooding, its cation exchange capacity (CEC) increased to twice that of its oxidized, unflooded state. Mössbauer spectroscopy showed an increase in smectite structural FeII upon reduction, which explained a part of the increase in CEC. The rest of the increase was attributed to the removal of iron oxyhydroxide coatings by reductive dissolution. The reduction and dissolution of oxides under the field conditions were substantiated by analysis of the surfaces of vermiculites buried in the Ap horizons of the cropped and the non‐cropped soils. The redox‐induced CEC changes were found to be reversible after 22 cycles of rice cropping. Nevertheless, the structural Fe and free Fe contents of the rice field Ap horizon were less than those of soil in uncropped neighbouring land, suggesting that inundation induced weathering and eluviation of the minerals. The observed changes in CEC and related redox reactions may substantially modify proton, anion and cation balances in intermittently flooded soils.

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