Microstructure of Al-substituted goethite and its adsorption performance for Pb(II) and As(V)

Naturally occurring goethite commonly undergoes Al-substitution, while how changes in microstructure induced by Al-substitution affect the interactive reaction of Pb(II) or As(V) at the goethite-water interface remains poorly understood. This study reveals the structural properties of Al-substituted goethite and its adsorption behavior for Pb(II) and As(V) by multiple characterization techniques and Charge Distribution-Multisite Surface Complexation (CD-MUSIC) modeling. Al-substitution caused an obvious decrease in the length-to-width ratio in goethite particles and a slight decrease in the proportion of (110) facets. The presence of Al-O sites and higher surface roughness induced by Al-substitution contributed to a higher inner Stern layer capacitance (C₁) and surface charge density of goethite. CD-MUSIC modeling results further revealed that the affinity constant of Pb(II) complex (log K_Pb) at the goethite-water interface and the adsorption capacity of goethite for Pb(II) decreased with increasing amount of Al-substitution, while an opposite tendency was observed for As(V) adsorption. The dominant species of both Pb(II) and As(V) on goethite were bidentate complexes, and Al-substitution had a minor impact on the abundance of Pb(II) and As(V) complexes on the surface of goethite. Overall, these experimental and modeling results provide new and important insights into the interfacial reactivity of Al-substituted goethite and facilitate the prediction of the environmental fate of heavy metals.