Manganese oxide application reduces cadmium bioavailability in rice rhizosphere: Insights from desorption kinetics and high-resolution imaging

Cadmium (Cd) contamination in paddy soils threatens global food safety. While manganese (Mn)-based materials show promise in reducing soil Cd bioavailability, their efficacy requires further evaluation. Traditional ex situ sampling methods often overlook metal desorption kinetics and rhizosphere biochemical heterogeneity, potentially misinterpreting Mn's regulatory influence on Cd dynamics. This study employed in situ monitoring tools, including diffusive gradients in thin-films (DGT) measurements, DIFS (DGT-induced fluxes in soils) modeling, and high-resolution DGT and planar optode (PO) imaging, to assess the impact of two Mn oxides (MnO₂ and Mn₂O₃) on Cd bioavailability in rice rhizosphere. Application of MnO₂ and Mn₂O₃ reduced bioavailable Cd by 28.9 % and 15.3 %, respectively, attributed to elevated soil Mn and Fe levels fostering Cd immobilization. DGT-DIFS results revealed that Mn oxide application prolonged Cd replenishment time and reduced its desorption rate from soil solids. PO imaging identified pH heterogeneity in rice rhizosphere, confirming that Mn oxides mediated Cd bioavailability reduction by increasing pH. High-resolution DGT imaging revealed distinct spatial distribution patterns of Cd, Mn, and Fe fluxes, demonstrating Mn's inhibitory effects on Cd bioavailability. These findings highlight the potential of Mn oxides to mitigate Cd uptake by rice, offering a promising strategy for managing Cd-contaminated soils.