[S,S]-EDDS Ligand as a Soil Solubilizer of Fe, Mn, Zn, and Cu to Improve Plant Nutrition in Deficient Soils.

The deficiencies of iron, manganese, zinc, and copper in calcareous soils are a worldwide problem affecting plant growth and fruit quality, usually minimized by the application of recalcitrant synthetic metal chelates. Biodegradable ligand [S,S]-EDDS is an eco-friendly substitute. This study investigates the capacity of [S,S]-EDDS to mobilize micronutrients from agronomic soils and improve plant nutrition. A batch and a plant experiment (Phaseolus vulgaris cv. Black Pole) with three agronomic soils was conducted to monitor the micronutrients solubilized by [S,S]-EDDS, the ligand degradation, and plant uptake. The results demonstrated the high capacity of [S,S]-EDDS to solubilize Fe and other micronutrients related to its chemical behavior and the enhancement of plant nutrition. The best results were shown in sandy-clay soil with low Fe, typically found in the Mediterranean areas. The results support the direct application of the ligand to soils and a possible biotechnological application of the ligand-producer bacteria.

Iron and Humic Acid Accumulation on Soybean Roots Fertilized with Leonardite Iron Humates under Calcareous Conditions.

Iron humates are eco-friendly fertilizers that are less efficient than iron synthetic chelates at correcting iron chlorosis. The aim of this work was to improve the efficiency of a leonardite iron humate (LIH), by studying the relationship among humic acid (HA) accumulation, iron biomineralization on soybean roots, and iron nutrition in soybean plants under calcareous conditions. Two hydroponic experiments were performed: a short-term bioassay (21 days) with several doses (10, 20, 50, and 100 µmol of Fe pot-1) of LIH applied once a week and a long-term bioassay (60 days) with just one application of LIH (250 µmol of Fe pot-1). When LIH was applied several times, it precipitated on the root, blocking the cell wall pores and reducing iron transport in plants, while these effects decreased when LIH was applied just once, thus favoring iron uptake by the plants and avoiding HA accumulation. Jarosite was observed on the surface of soybean roots.

Isotope pattern deconvolution as a tool to study iron metabolism in plants.

Isotope pattern deconvolution is a mathematical technique for isolating distinct isotope signatures from mixtures of natural abundance and enriched tracers. In iron metabolism studies measurement of all four isotopes of the element by high-resolution multicollector or collision cell ICP-MS allows the determination of the tracer/tracee ratio with simultaneous internal mass bias correction and lower uncertainties. This technique was applied here for the first time to study iron uptake by cucumber plants using 57Fe-enriched iron chelates of the o,o and o,p isomers of ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA) and ethylenediamine tetraacetic acid (EDTA). Samples of root, stem, leaves, and xylem sap, after exposure of the cucumber plants to the mentioned 57Fe chelates, were collected, dried, and digested using nitric acid. The isotopic composition of iron in the samples was measured by ICP-MS using a high-resolution multicollector instrument. Mass bias correction was computed using both a natural abundance iron standard and by internal correction using isotope pattern deconvolution. It was observed that, for plants with low 57Fe enrichment, isotope pattern deconvolution provided lower tracer/tracee ratio uncertainties than the traditional method applying external mass bias correction. The total amount of the element in the plants was determined by isotope dilution analysis, using a collision cell quadrupole ICP-MS instrument, after addition of 57Fe or natural abundance Fe in a known amount which depended on the isotopic composition of the sample.

Comparison of two analytical methods for the evaluation of the complexed metal in fertilizers and the complexing capacity of complexing agents.

The aim of this research is to develop an analytical methodology for the determination of complexed element in fertilizers and, then, to obtain an adequate criteria for the inclusion of these products in European Regulations on Fertilizers. This paper compares the CEN method EN 13366:2001, based on the retention of the cations into a sulfonated resin, and an AOAC modified method, based on the precipitation of the inorganic forms at pH 9. A limited interlaboratory trial was carried out to demonstrate the applicability of the AOAC modified method and to study the effect of the removal of organic compounds and the addition of a matrix modifier solution before the element quantification. Then, a global interlaboratory trial was developed to evaluate the validation and quality parameters of the method. As a second objective, the AOAC modified method was applied to the determination of the complexing capacity of complexing agents based on lignosulfonates and amino acids. The AOAC modified method was the choice methodology because it is adequate for the determination of complexing capacity of micronutrients in fertilizer.

Synthesis of o,p-EDDHA and its detection as the main impurity in o,o-EDDHA commercial iron chelates.

Ethylenediamine-N,N'bis(o-hydroxyphenyl)acetic acid (o,o-EDDHA) is one of the most efficient iron chelates employed to relieve iron chlorosis in plants. However, the presence of positional isomers of EDDHA in commercial iron chelates has been recently demonstrated, and among them, it has been claimed that ethylenediamine-N(o-hydroxyphenylacetic)-N'(p-hydroxyphenylacetic) acid (o,p-EDDHA) is the main impurity present in EDDHA fertilizers. Here we report the preparation of o,p-EDDHA, a compound whose synthesis had not been previously reported. The synthetic o,p-EDDHA is able to form ferric complexes, and it has been used as a standard in the analysis of the impurities of commercial iron fertilizers. The presence of o,p-EDDHA/Fe(3+) in commercial samples has been unambiguously demonstrated by HPLC.