Iron reduction and changes in cation exchange capacity in intermittently waterlogged soil

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 Fe^II 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.