Rapidly reducing cadmium from contaminated farmland soil by novel magnetic recyclable Fe3O4/mercapto-functionalized attapulgite beads

Abstract

Reducing cadmium (Cd) content from contaminated farmland soils remains a major challenge due to the difficulty in separating commonly used adsorbents from soils. This study synthesized novel millimeter-sized magnetic Fe3O4/mercapto-functionalized attapulgite beads (MFBs) through a facile one-step gelation process incorporating alginate. The MFBs inherit the environmental stability of alginate and enhance its mechanical strength by hybridizing Fe3O4 and clay mineral components. MFBs can be easily separated from flooded soils by magnets. When applied to 12 Cd-polluted paddy soils and 14 Cd-polluted upland soils, MFBs achieved Cd(II) removal rates ranging from 16.9% to 62.2% and 9.8%–54.6%, respectively, within a 12-h period. The MFBs predominantly targeted the exchangeable and acid soluble, and reducible fractions of Cd, with significantly enhanced removal efficiencies in paddy soils compared to upland soils. Notably, MFBs exhibited superior adsorption performance in soils with lower pH and organic matter (OM) content, where the bioavailability and mobility of Cd are heightened. The reduction of Cd content by MFBs is a sustainable and safe method, as it permanently removes the bioavailable Cd from soil, rather than temporarily reducing its bioavailability. The functional groups such as –SH, –OH, present in attapulgite and alginate of MFBs, played a crucial role in Cd(II) adsorption. Additionally, attapulgite and zeolite provided a porous matrix structure that further enhanced Cd(II) adsorption. The results of X-ray photoelectron spectroscopy suggested that both chemical precipitation and surface complexation contributed to Cd(II) removal. The MFBs maintained 87.6% Cd removal efficiency after 5 regeneration cycles. The surface of the MFBs exposed new adsorption sites and increased the specific surface area during multiple cycles with Cd-contaminated soil. This suggests that MFBs treatment with magnetic retrieval is a potentially effective pathway for the rapid removal of Cd from contaminated farmland soils.