Javier Erro

Determination of organic acids in tissues and exudates of maize, lupin, and chickpea by high-performance liquid chromatography-tandem mass spectrometry.

This article describes a fast and simple methodology for the extraction and determination of organic acids in tissues and root exudates of maize, lupin, and chickpea by LC/MS/MS. Its main advantage is that it does not require sample prepurification before HPLC analysis or sample derivatization to improve sensibility. The results obtained showed good precision and accuracy, a recovery close to 100%, and no significant matrix effect. Moreover, the sensibility of the method is in general better than that of previously described methodologies, with detection limits between 15 and 900 pg injected.

Theoretical chemical characterization of phosphate‐metal–humic complexes and relationships with their effects on both phosphorus soil fixation and phosphorus availability for plants

BACKGROUND Previous studies showed that phosphate can be complexed by humic acids (HA) through stable metal (M) bridges (PMHA). We studied the thermodynamic properties of PMHA and their relationships with the ability of PMHA to both decrease soil P fixation and increase P availability for plants. With this aim, we studied the theoretical stability of PFeHA, PAlHA and PCaHA by molecular modelling methods in relation to the degree and intensity of P absorption in soils and the ability of plants to take up complexed P. RESULTS A density functional theory (DFT) quantum chemical study enabled us to obtain stable structures for the three PMHA complexes in water solution. The theoretical stabilities (ΔG⁰) were consistent with that for apparent stability obtained by Scatchard method, PFeHA ≥ PAlHA > PCaHA, though the differences were clearer by the DFT method. Also the reduction of soil P fixation and the release of P from PMHA in the presence of an anionic resin confirmed the stability order of the different PMHA. Plant studies confirmed the ability of diverse plant species to take up both P and metal complexed in PMHA. CONCLUSION The results indicated the potential efficiency of PMHA-based fertilizers to optimize P fertilization for crops cultivated in soils with high P fixation ability.

Organic Complexed Superphosphates (CSP): Physicochemical Characterization and Agronomical Properties

A new type of superphosphate (organic complexed superphosphate (CSP)) has been developed by the introduction of organic chelating agents, preferably a humic acid (HA), into the chemical reaction of single superphosphate (SSP) production. This modification yielded a product containing monocalcium phosphate complexed by the chelating organic agent through Ca bridges. Theoretically, the presence of these monocalcium-phosphate-humic complexes (MPHC) inhibits phosphate fixation in soil, thus increasing P fertilizer efficiency. This study investigateed the structural and functional features of CSP fertilizers produced employing diverse HA with different structural features. To this end were used complementary analytical techniques: solid-phase ³¹P NMR, ¹³C NMR, laser-confocal microscopy, X-ray diffraction, and molecular modeling. Finally, the agronomical efficiency of four CSP have been compared with that of SSP as P sources for wheat plants grown in both alkaline and acidic soils in greenhouse pot trials under controlled conditions. The results obtained from the diverse analytical studies showed the formation of MPHC in CSP. Plant-soil studies showed that CSP products were more efficient than SSP in providing available phosphate for wheat plants cultivated in various soils with different physicochemical features. This fact is probably associated with the ability of CSP complexes to inhibit phosphate fixation in soil.

31P NMR characterization and efficiency of new types of water-insoluble phosphate fertilizers to supply plant-available phosphorus in diverse soil types.

Hydroponic plant experiments demonstrated the efficiency of a type of humic acid-based water-insoluble phosphate fertilizers, named rhizosphere controlled fertilizers (RCF), to supply available phosphorus (P) to different plant species. This effect was well correlated to the root release of specific organic acids. In this context, the aims of this study are (i) to study the chemical nature of RCF using solid-state (31)P NMR and (ii) to evaluate the real efficiency of RCF matrix as a source of P for wheat plants cultivated in an alkaline and acid soil in comparison with traditional water-soluble (simple superphosphate, SSP) and water-insoluble (dicalcium phosphate, DCP) P fertilizers. The (31)P NMR study revealed the formation of multimetal (double and triple, MgZn and/or MgZnCa) phosphates associated with chelating groups of the humic acid through the formation of metal bridges. With regard to P fertilizer efficiency, the results obtained show that the RCF matrix produced higher plant yields than SSP in both types of soil, with DCP and the water-insoluble fraction from the RCF matrix (WI) exhibiting the best results in the alkaline soil. By contrast, in the acid soil, DCP showed very low efficiency, WI performed on a par with SSP, and RCF exhibited the highest efficiency, thus suggesting a protector effect of humic acid from soil fixation.

Structural Characterization of Anion–Calcium–Humate Complexes in Phosphate‐based Fertilizers

Fertilizers based on phosphate-metal-humate complexes are a new family of compounds that represents a more sustainable and bioavailable phosphorus source. The characterization of this type of complex by using solid (31)P NMR in several fertilizers, based on single superphosphate (SSP) and triple superphosphate (TSP) matrices, yielded surprising and unexpected trends in the intensity and fine structure of the (31)P NMR peaks. Computational chemistry methods allowed the characterization of phosphate-calcium-humate complexes in both SSP and TSP matrices, but also predicted the formation of a stable sulfate-calcium-humate complex in the SSP fertilizers, which has not been described previously. The stability of this complex has been confirmed by using ultrafiltration techniques. Preference towards the humic substance for the sulfate-metal phase in SSP allowed the explanation of the opposing trends that were observed in the experimental (31)P NMR spectra of SSP and TSP samples. Additionally, computational chemistry has provided an assignment of the (31)P NMR signals to different phosphate ligands as well as valuable information about the relative strength of the phosphate-calcium interactions within the crystals.

Incorporation of humic-derived active molecules into compound NPK granulated fertilizers: main technical difficulties and potential solutions

Numerous studies carried out both in open field and laboratory scale have provided experimental evidence for a beneficial action of humic substances (HS) on plant growth and mineral nutrition. In fact, many products containing diverse concentrations of humic substances, mainly humic and fulvic acids, are marketed as plant growth enhancers all over the world. However, the incorporation of molecules containing humic substances into the granules of compound NPK fertilizers is not a common practice mainly due to technical difficulties and problems associated with the manufacture process of these mineral fertilizers. These problems are normally linked to the potential deleterious effects of granulation conditions (principally, heat and pH) on the structure and properties of molecules containing humic substances. In this review, we discuss several strategies for the incorporation of active molecules containing humic substances into granules of NPK compound fertilizers as well as the main constraints that have to be considered in this process, which normally depend on the agronomical results intended with the preparation of special humic-containing NPK compound fertilizers. We also discuss why, in our opinion, the beneficial action of HS in NPK compound fertilizers is more related to the “so called” indirect effects of HS on plant growth than to the “so called” direct effects.Graphical abstractLocalization of humic-calcium-phosphate based NPK fertilizer granule into the rhizosphere of maize plants cultivated in a calcareous soil

New Amphiphilic Composite for Preparing Efficient Coated Potassium-Fertilizers for Top-Dressing Fertilization of Annual Crops

This study describes the efficiency of a new coating material for preparing granulated potassium-fertilizers with a potassium release to the soil solution sensitive to rainfall intensity. The composite is prepared by reaction of an alkyd-resin with cement in the absence of water. The complementary use of diverse analytical techniques showed that the presence of the cement fraction induced alkyd resin reticulation and gradual cement-resin hardening. Scanning electron microscopy revealed the formation of micro and nanopores within cement-clusters, whose water permeability is affected by the resin reticulation and amphiphilic character. Potassium release was evaluated in water, soil-columns, and in soil-plant trials in pots and open-field. Agronomic results were consistent with potassium release rates obtained in water solution and soil columns. The composite-coated potassium fertilizer was more efficient than the noncoated one in providing plant available potassium, with this effect being dependent on water presence in soil.