Modeling the effects of humic acid and anoxic condition on phosphate adsorption onto goethite

Low redox potential in flooded soils may affect phosphate bioavailability by reducing iron oxides or formation of new minerals. To investigate phosphate behavior in anoxic conditions, goethite was selected as a soil model and coated by humic acid (HA) and sodium borohydride was used as a reducing agent. Adsorption experiments were conducted in 0.1 M NaNO₃ as a function of pH in oxic (Eh = +254 to +448 mV) and suboxic (Eh = -162 to +167 mV) conditions for four phosphate concentrations (0.05-0.8 mM). CD-MUSIC and NOM-CD models in combination with Extended Stern model were used to describe the experimental data. Results show that by increasing pH and carbon content in the organo-mineral composites, the released phosphate to the solution increases in both oxic and suboxic conditions. In suboxic conditions, as a result of sodium borohydride dissociation in water and consequently boron release to the solution, at high loading of boron and low loading of phosphate, boron can compete with phosphate for the surface reactive sites and decrease its adsorption. On the other hand, ferrous iron can attenuate boron effect and promote phosphate adsorption. The results indicated that goethite surface is resistant to the reductive transformation that may occur at relatively low redox potential due to its high crystalline character and thermodynamic stability. HA may, however, promote the formation of amorphous iron phases, which consequently might induce phosphate adsorption in OM-mineral composites. The derived affinity constants in oxic conditions described the experimental data of suboxic conditions reasonably well.