Abstract

Vivianite [Fe3(PO4)2·8H2O] is easily oxidized in the presence of air. In this work, we studied the oxidation and incongruent dissolution of vivianite in a calcareous medium containing an anion-exchange resin (AER) that acted as a sink for phosphate. Freshly prepared vivianite suspensions with calcite sand and an AER membrane were oxidized and stirred by bubbling air or CO2-free O2. Experiments were finished when oxidation rate and P removal by the AER became slow, which was at 53 days (air system) or 28 days (CO2free O2 system). At these times, the respective values of the Fe(II)/total Fe ratio were 0.29 and 0.12, and the respective values of the atomic P/Fe ratio were 0.15 and 0.11. The final product of the oxidation was poorly crystalline lepidocrocite in the form of thin (1–5 nm), irregular lamellae that were soluble in acid oxalate. The unit-cell edge lengths of this lepidocrocite were a = 0.3117, b = 1.2572, and c = 0.3870, vs. a = 0.3071, b = 1.2520 and c = 0.3873 nm for the reference lepidocrocite. The lepidocrocite lamellae contained occluded P (P/Fe atomic ratio = 0.03–0.04). The results of this and a previous study made us hypothesize that this occluded P is structural and occupies tetrahedral sites adjacent to the empty octahedral sites in the sheets extending on {010}.

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