The aim of this review is to describe the main physicochemical characteristics of diverse types of humic‐metal‐phosphate acid complexes. The effects of these complexes on phosphorus (P) fixation in soils with different pH values and physicochemical features and on plant phosphorus uptake are also discussed. Humic‐metal‐phosphate complexes have apparent stability constants in the same range as those of metal‐humic complexes, in solutions with diverse pH and ionic‐strength values. Likewise, the molecular‐size distribution of humic‐metal‐phosphate complexes as a function of pH is similar to that of potassium or sodium humates and metal‐humic complexes. Humic‐metal‐phosphate complexes are able to decrease phosphate fixation in soils and increase plant growth and phosphate uptake. Phosphorus fertilizers containing humic‐metal‐phosphate complexes proved to be efficient to improve plant growth and P uptake with respect to conventional fertilizers such as single superphosphate. The values of parameters related to plant phosphorus‐utilization efficiency (PUt E) suggest that the regulation of root acquisition of phosphate from these complexes could involve the interregulation of a system for the optimization of metabolic P utilization in the shoot and another system involving stress responses of roots under phosphorus deficiency.

Size distribution, maximum complexing ability, and stability constants for phosphate-metal-humic (PO43--M-HA) complexes involving two trivalent (Fe and Al) and five divalent metal (M) bridges (Zn, Cu, Mn, Ca, and Mg) were investigated at the pH values 4, 6, and 8. Results highlighted the existing competition between metal-humic acid (M-HA) aggregation and the formation of PO43--M-HA complexes. However, the fact that only a very low fraction of complexed metal is involved in PO43- fixation seems to be related to the existence of specific electronic and/or steric requirements in the binding site in the metal-humic complex. The importance of the ionic form of phosphate (H2PO4- or HPO42-) and the involvement of phenolic and especially carboxylic groups in the phosphate binding are discussed. Finally, the order of stability obtained for PO43--M-HA complexes was similar to that of M-HA complexes. This result suggests that PO43--M-HA might play a significant role in the dynamics of phosphorus in certain soil types.

The results indicated the potential efficiency of PMHA-based fertilizers to optimize P fertilization for crops cultivated in soils with high P fixation ability.

The aim of this work is to study the suitability of the complementary use of ultrafiltration (UF) and the interaction with an anion-exchange resin (AR) to characterize of phosphate-metal-humic complexes in solution. The results indicate that a methodological approach consisting of the validation and calibration of the AR method by the UF method and the further use of the AR method is suitable for characterizing phosphate-metal complexes. Such an approach has proven to be useful for calculating the phosphate maximum binding capacity of iron-humic complexes and stability constants. It might also be used to obtain valuable purified phosphate-metal-humic complexes for further structural characterization.

Previous studies demonstrated the formation of stable phosphate-metal-humic complexes in solution. These studies, however, indicated that the proportion of complexed metal that intervenes in phosphate fixation is rather low. In this study we investigate the possible structural and electronic features of the binding site involved in phosphate fixation in metal-humic complexes that could explain this fact. To this end, we have studied phosphate-metal-humic complexes involving Fe(III), Al(III), and Zn(II) using three complementary techniques: infrared spectroscopy (FTIR), fluorescence, and molecular modeling. The FTIR study indicated that, in the case of those complexes involving Fe and Zn phosphate, fixation is associated with a stabilization of the metal-carboxylate bond. In the case of Al this effect is less clear. This effect of phosphate fixation on the characteristics of the metal-humic binding site was also supported by the results obtained in the Fluorescence study, which showed significant changes in the quenching effect normally associated with metal complexation in humic substances upon phosphate fixation. Finally, the molecular modeling study revealed that the stability of phosphate-metal-humic complexes is inversely related to the stability of the metal-humic interaction. This result could explain why only a relatively low proportion of humic complexed metal is involved in phosphate fixation.