Immobilization of cadmium in river sediments by different modified nanoscale zero-valent iron: performance, mechanisms, and Fe dissolution.

Modified nanoscale zero-valent iron (NZVI) exhibited great potential for the remediation of heavy metal contaminated river sediments, but its mechanisms and environmental risks are still unclear. This study systematically discussed the performance and the mechanisms of modified NZVI materials, i.e., sodium alginate-coated NZVI (SNZVI), rhamnolipid-coated NZVI (RNZVI), and graphene oxide-loaded NZVI (GNZVI), for the stabilization of Cd in sediment, with the exploration of their stability to Cd at various pH values and Fe dissolution rate. Compared with the control, the toxicity characteristic leaching procedure (TCLP) leachable Cd decreased by 52.66-96.28%, and the physiologically based extraction test (PBET) extractable Cd decreased by 44.68-70.21% after 56 days of incubation with the immobilization efficiency varying according to GNZVI > RNZVI > SNZVI > NZVI. Besides, the adsorption behavior of Cd on materials was fitted with the Freundlich model and classified as an endothermic, spontaneous, and chemical adsorption process. SEM-EDX, XRD, and FTIR results verified that the stabilization mechanisms of Cd were principally based on the adsorption, complexation of Cd with secondary Fe minerals (including FeO, γ-FeO, and γ-FeOOH) and precipitation (Cd(OH)). From the risk assessment results, it was observed that the materials were favorable for Cd stabilization at a pH range from 7 to 11, meanwhile, the leaching concentration of Fe in the overlying water was detected below the limit value. These findings pave the way to developing an effective strategy to remediate Cd contaminated river sediments.