Cadmium speciation and release kinetics in a paddy soil as affected by soil amendments and flooding-draining cycle

Cadmium bioavailability in paddy soils is strongly affected by flooding-draining cycle. In this study, we used synchrotron-based X-ray absorption spectroscopy and a stirred-flow method to investigate the effects of flooding-draining and amendments of CaCO₃ and CaSO₄ on Cd speciation and release kinetics from a Cd-spiked paddy soil (total Cd concentration of 165 mg kg^-1). Extended X-ray absorption fine structure analysis showed that Cd was predominantly bound to non-iron-clay minerals (e.g. Cd-kaolinite, Cd-illite, and Cd-montmorillonite, accounting for 60-100%) in the air-dried soil and 1- or 7-day flooded samples. After prolonged flooding (30 and 120 days), Cd-iron mineral complexes (e.g. Cd bound to ferrihydrite and goethite) became the predominant species (accounting for 52-100%). Stirred-flow kinetic analysis showed that both prolonged flooding and the amendments with CaCO₃ and CaSO₄ decreased the maximum amount and the rate coefficient of Cd release. However, the effect of prolonged flooding was reversed after a short period of draining, indicating that although Cd was immobilized during flooding, it became mobile rapidly after the soil was drained, possibly due to pH decrease and rapid oxidation of CdS. The effects of the amendments on Cd uptake in rice plants were tested in a pot experiment using the same paddy soil without Cd spiking (total Cd 2.1 mg kg^-1). Amendment with CaCO₃ and, to a lesser extent, CaSO₄, decreased the Cd accumulation in two cultivars of rice. The combination of CaCO₃ amendment and a low Cd accumulating cultivar was effective at limiting grain Cd concentration to below the 0.2 mg kg^-1 limit.