Interaction of fulvic acid with soil organo-mineral nano-aggregates and corresponding phosphate release

For more insight into the interaction of natural organic matter (NOM) with metal (hydr)oxides and oxyanions, the adsorption of added fulvic acid (FA) and the corresponding release of phosphate (PO4) were studied for a series of agricultural soils (∼0 – 25 cm), strongly varying in soil properties. Interpretation of the data with surface complexation modeling using the NOM-CD model applied in a dual-phase mode shows that the adsorption of added FA, in contrast to PO4, is restricted to the external surfaces of nano-aggregates. The adsorption is relatively weak and pH-independent, due to its competition with the native NOM of the organo-mineral phase. At low pH, the functional groups of both added FA and native NOM shift in the interface towards the soil oxide surfaces, making both a good competitor for adsorbed phosphate, resulting in a higher amount of phosphate being released. With an increase in pH, the competition becomes weaker. As a result, more phosphate is bound and less is released when FA is added. Our surface complexation modeling points to the existence of organo-mineral nano-aggregates with sizes of >∼10 – 270 nm, which depends on the total reactive surface area of the soil. Our findings imply that organic amendments containing FA equilibrate with only a portion of the total reactive surface area. In acidic soils, the addition of such organic amendments will be more effective in solubilizing phosphate, which is beneficial from a plant nutrition perspective, but simultaneously it may also contribute more to environmental eutrophication.