Dissolution of Poorly Crystalline Iron Oxides in Soils by EDTA and Oxalate

Poorly crystalline iron oxides in soils are often estimated by 2 hours oxalate extraction at pH 3 and less often by 3–7 months EDTA extraction at pH 7.5–10.5. Calculated solubility products (Ksp) of iron oxides in equilibrium with EDTA and oxalate showed EDTA to dissolve only iron oxides with Ksp > 10^?40-10^?41 at pH > 10, whereas at pH 3 oxalate (and EDTA) should theoretically dissolve all iron oxides. The different pHs could largely account for the great difference in extraction speed between the two methods. Although EDTA and oxalate seem to act by surface complexation, where the adsorbed ligand by attenuating lattice Fe-O bonds causes iron detachment, the mechanisms are considered to be different. Possibly EDTA forms tetranuclear surface complexes, which are considered to inhibit dissolution of well crystallized but not poorly crystallized iron oxides due to differences in bond strengths. Oxalate forming binuclear and mononuclear surface complexes can probably also act as an electron bridge between iron(II) in solution and surface iron(III) leading to iron(II) catalyzed dissolution of iron oxides. This mechanism is obviously of particular importance in the dissolution of magnetite and maghemite. Despite the great theoretical differences the published methods with EDTA and oxalate dissolve comparable amounts of iron from many soils and the dissolved iron corresponds to poorly crystalline (highly reactive) iron oxides, mainly ferrihydrite.