Selective adsorption of various phosphorus species coexistence in water-soluble ammonium polyphosphate on goethite: Experimental investigation and molecular dynamics simulation

Abstract

The geochemical processes of polyphosphates (poly-Ps) are important for phosphorus (P) management and environmental protection. Water-soluble ammonium polyphosphate (APP) containing various P species has been increasingly used as an alternative P-fertilizer. The various P species coexistence and the chelation of poly-Ps with mental would trigger the P's competitive adsorption and affect the APP's adsorption intensity on goethite, compared to single orthophosphate (P₁). P adsorption behaviors of APP1 with two P species and APP2 with seven P species on goethite were investigated via batch experiments in comparison to the traditional P-fertilizer of mono-ammonium phosphate (MAP). Coadsorption of P₁ and pyrophosphate (P₂) on goethite was investigated by molecular dynamics (MD) simulation. The more Fe³⁺ dissolved from goethite as a bridge due to the chelation of poly-Ps in APP and contributed to the stronger APP adsorption on goethite compared with MAP. Ion chromatography and spectral analysis showed P₁ and P₂ in APP were mainly adsorbed by goethite via mainly forming bidentate complexes. The goethite preferentially adsorbed P₁ at lower APP concentration but increased the poly-Ps' adsorption at higher APP concentration. MD simulation showed that electrostatic interaction and hydrogen bonds played a key role in water-phosphates-goethite systems. The P₁ pre-adsorbed on goethite could be replaced by P₂ at high P₂ concentration. The results develop new insights regarding the selective adsorption of various P species coexistence in goethite-rich environments.

Keywords: Ammonium polyphosphate; Goethite; Ion chromatography; Molecular dynamics simulation; Selective adsorption.