Multistage stabilization of Cd, Pb, Zn, Cu and As in contaminated soil by phosphorus-coated nZVI layered composite materials: characteristics, process and mechanism

This study developed a shell-like slow-release material, PF@ST/Fe-0.5, by encapsulating nanoscale zero-valent iron composites (NZC) with phosphate fertilizer (PF) and a starch binder (ST). The material dissolved in soil in stages, first releasing P and Ca to increase the soil pH from 4.95 to 7.14. This was followed by the formation of phosphates and hydroxides precipitates with Pb, Cu, Zn, and Cd in soil, reducing their bioavailable forms by 81.73 %, 79.58 %, 91.05 %, and 86.47 %, respectively. The process also involved the competitive adsorption between PO₄^3-/HPO₄^2- and arsenate/arsenite led to the release of specifically adsorbed arsenic, increasing the probability of reaction with the material. Afterwards, the exposure of the NZC core reacted with arsenate/arsenite to form ferric arsenates, thus reducing the content of bioavailable arsenic in the soil by 73.57 %. Excess PO₄^3- and alkali metal cations were captured and mineralized by the iron (hydro) oxides and reactive silicates in NZC, enhancing the remediation effect. Furthermore, the wet-dry alternation test had demonstrated the adaptability of PF@ST/Fe-0.5 to the rainy dry-wet soil environment in Yunnan, which enabled the bioavailable content of As, Pb, Cu, Zn, and Cd decreased by 71.2 %, 94.8 %, 84.1 %, 79.8 %, and 83.9 %, respectively. The layered structure minimized internal reactive substance consumption and protected the internal nZVI from oxidation. The phased release of phosphate and Fe⁰ stabilized Pb, Cu, Zn, and Cd, enhancing As stabilization and providing a new perspective for the synchronous stabilization of soil contaminated.