Significantly enhanced P release from vivianite as a fertilizer in rhizospheric soil: Effects of citrate

The use of vivianite (Fe₃(PO₄)₂∙8H₂O) as a slow-release P fertilizer in agriculture could be a promising way for the utilization of the recovered vivianite products from sewage treatment systems but the efficiency of vivianite-P release in the rhizospheric soil was yet unclear. In this work the dissolution of vivianite was investigated under anoxic and aerobic conditions with the focus on the effects of citrate as a common organic matter in the rhizosphere by tracking the kinetics of P release and the variations of aqueous and solid phases. The results show that citrate effectively induced the dissolution of vivianite particles at pH 6 with simultaneous release of Fe and PO₄-P. The enhancement of vivianite dissolution was positively correlated to the concentrations of citrate with complete dissolution observed when citrate was above 6 mM. Compared with anoxic conditions, aerobic conditions further enhanced the dissolution of vivianite to some extent, which could be partially attributed to the oxidation and removal of aqueous Fe^II in the solution that drove the equilibrium towards dissolution. In the presence of 2 mM citrate, the decrease in pH from 6.0 to 4.0 enhanced the vivianite-P release by 56.1%, indicating the pH dependence of the citrate-induced vivianite dissolution. This study has shown that the efficiency of P release from vivianite products as a fertilizer varies largely under different physico-chemical conditions in the rhizospheric microenvironment, which is critical for determining the dosage of vivianite for a specific soil.