Influence of the soil/solution ratio, interaction time, and extractant on the evaluation of iron chelate sorption/desorption by soils

Synthetic Fe chelates are the most efficient agricultural practice to control Fe deficiency in crops, EDTA/Fe3+ and o,o-EDDHA/Fe3+ being the most commonly used. Their efficacy as Fe sources and carriers in soils can be severely limited by their retention on it. The aim of this work is to evaluate the possible bias introduced in the studies of the iron chelate retention by soils. For that purpose, results obtained for EDTA and EDDHA iron chelates from two batch studies with different soil/solution ratios were compared with data obtained for a leaching column experiment. Moreover, different extractants were tested to study the o,o-EDDHA/Fe3+ and o,p-EDDHA/Fe3+ desorption from a calcareous soil, and also the effect of the interaction time in their retention process has been evaluated. In summary, the mobility through a calcareous soil of the studied iron chelates differs greatly depending on the type of iron chelate and also on the procedure used to evaluate the retention and the soil/solution ratio used. In general, the leaching column method is preferred because the achieved conclusions are more representative of the natural conditions, but batch methods are very useful as a preliminary experiment, especially one with a high soil/solution ratio. The iron chelate desorption could be quantified by using a sequential extraction with water, sodium sulfate, and DTPA as extractants. Under the experimental conditions used in this study, o,o-EDDHA/Fe3+ retention increased with interaction time.     

Structure and fertilizer properties of byproducts formed in the synthesis of EDDHA

The synthesis of commercial EDDHA produces o,o-EDDHA as the main reaction product, together with a mixture of regioisomers (o,p-EDDHA and p,p-EDDHA) and other unknown byproducts also able to complex Fe3+. These compounds have been obtained by direct synthesis, and their structures have been determined by ESI-MS analysis as oligomeric EDDHA-like products, formed by polysubstitution in the phenolic rings. Short-term experiments show that the iron complexes of samples enriched in these oligomeric byproducts have adequate stability in solution, but a significant amount of them is lost after interaction with soils and soil materials. Mildly chlorotic cucumber plants are able to reduce iron better from o,p-EDDHA/Fe3+ than from the iron complexes of the oligomeric byproducts. In hydroponics, the chlorotic soybean susceptible plants have a lower potential for Fe absorption from these byproducts than from o,o-EDDHA/Fe3+ and from o,p-EDDHA/Fe3+. In the studied conditions, the iron chelates of EDDHA byproducts do not have the long-lasting effect shown by o,o-EDDHA/Fe3+ and present a less efficient fast-action effect than the o,p-EDDHA/Fe3+.     

Determination of Fe2+ in Rice Leaves (Oryza sativa L.) by Using the Chelator BPDS Alone or Combined with the Chelator EDTA

Abstract

Iron toxicity is a problem in many areas of wetland rice. Since Fe²⁺ is considered to be the toxic form of iron, the objective of this research was to determine the Fe²⁺ concentration in rice leaves using the chelator bathophenanthroline disulfonate (BPDS), disodium salt alone or combined with the chelator ethylenediaminetetraacetate (EDTA), disodium salt, where BPDS should solely chelate the Fe²⁺ and EDTA chelate only Fe³⁺. Thus, the combination of these chelators should stabilize the Fe oxidation states. It was also tested whether the chelators BPDS and EDTA could stabilize the oxidation states of Fe during the extraction of rice leaves. Extractions of rice leaves were carried out using an 1 mM BPDS or BPDS‐EDTA extractant solution. To test the stabilization of the Fe oxidation states by the combination of BPDS with EDTA, the extraction solution for one part of the samples contained 0.07 mM Fe³⁺. An extraction without plant material as control was also taken into consideration. The results indicated that the chelators were able to stabilize the oxidation states of Fe in the control (extraction without plant material). However, in the presence of plant material, Fe³⁺ was partly reduced to Fe²⁺, i.e., the chelators could not stabilize the oxidation states of Fe. Accordingly, we concluded that the BPDS‐EDTA method may function for the Fe²⁺ determination in water and soil, but it is apparently not suited for rice leaves.     

Comparison of iron chelates and complexes supplied as foliar sprays and in nutrient solution to correct iron chlorosis of soybean

The application of synthetic chelates is the most efficient remedy for correcting iron (Fe) chlorosis. However, chelates are usually expensive and nondegradable products. Recently, new degradable chelates have been proposed for their use as Fe fertilizers. Also, Fe complexes cheaper than synthetic chelates and derived from natural products are also used to correct Fe deficiencies. Fifteen products, including five different synthetic chelates (Fe‐EDDS, Fe‐IDHA, and three Fe‐EDTA formulations) and ten natural complexes (humates, lignosulfonates, amino acids, glycoproteins, polyamines, citrate, and gluconate), have been compared when applied at low concentration to soybean (Glycine max L.) chlorotic plants grown in hydroponics under controlled conditions. In the first experiment, Fe compounds were applied to the nutrient solution, while in the second trial, Fe was foliar‐supplied. Dry matter, Fe concentration in shoots and roots, and SPAD values were used to evaluate the effectiveness of the Fe in the different products. In the nutrient‐solution experiment, synthetic chelates provided better plant growth, Fe concentration, and SPAD values than complexes. Among the Fe complexes, transferrin generally provided good plant responses, similar to those obtained with synthetic chelates. After foliar application, the highest regreening was observed for plants treated with synthetic chelates and amino acid complexes, but the translocation to roots only occurred for Fe lignosulfonate. Fe‐EDDS and Fe‐EDTA performed in a similar way when applied in nutrient solution or as foliar sprays.     

Demetalation of Fe, Mn, and Cu chelates and complexes: application to the NMR analysis of micronutrient fertilizers

The application of nuclear magnetic resonance (NMR) for the quality control of fertilizers based on Fe(3+), Mn(2+), and Cu(2+) chelates and complexes is precluded by the strong paramagnetism of metals. Recently, a method based on the use of ferrocyanide has been described to remove iron from commercial iron chelates based on the o,o-EDDHA [ethylenediamine-N,N'bis(2-hydroxyphenylacetic)acid] chelating agent for their analysis and quantification by NMR. The present work extended that procedure to other paramagnetic ions, manganese and copper, and other chelating, EDTA (ethylenediaminetetraacetic acid), IDHA [N-(1,2-dicarboxyethyl)-d,l-aspartic acid], and complexing agents, gluconate and heptagluconate. Results showed that the removal of the paramagnetic ions was complete, allowing us to obtain (1)H NMR spectra characterized by narrow peaks. The quantification of the ligands by NMR and high-performance liquid chromatography showed that their complete recovery was granted. The NMR analysis enabled detection and quantification of unknown impurities without the need of pure compounds as internal standards.     

Iron uptake by Caco-2 cells from NaFeEDTA and FeSO4: Effects of ascorbic acid, pH, and a Fe(II) chelating agent

Sodium iron(III) ethylenediaminetetraacetate (NaFeEDTA) has considerable promise as an iron fortificant because of its high bioavailability in foods containing iron absorption inhibitors. In this study, uptakes of iron from NaFeEDTA, FeSO4, and FeCl3 by Caco-2 cells were compared in the absence or presence of ascorbic acid (AA), an iron absorption enhancer; at selected pH levels; and in the absence or presence of an iron absorption inhibitor, bathophenanthroline disulfonic acid (BPDS). Ferritin formation in the cells was used as the indicator of iron uptake. Uptake from all three Fe sources was similar in the absence of AA. Adding AA at a 5:1 molar excess as compared to Fe increased uptake by 5.4-, 5.1-, and 2.8-fold for FeSO4, FeCl3, and NaFeEDTA, respectively. The smaller effect of AA on uptake from NaFeEDTA may be related to the higher solubility of NaFeEDTA and/or the strong binding affinity of EDTA for Fe3+, which may prevent AA and duodenal cytochrome b from effectively reducing EDTA-bound Fe. Uptake was inversely related to the pH of the media over a range of 5.8-7.2. Because uptake by DMT-1 is proton-coupled, the inverse relationship between pH and Fe uptake in all three iron sources suggests that they all follow the DMT-1 pathway into the cell. Adding BPDS to the media inhibited uptake from all three iron compounds equally. Because BPDS binds Fe2+ but not Fe3+ and because only Fe2+ is transported by DMT-1, the finding that BPDS inhibited uptake from NaFeEDTA suggests that at least some iron dissociates from EDTA and is reduced just as simple inorganic iron at the brush border membrane of the enterocyte. Taken together, these results suggest that uptake of iron from NaFeEDTA by intestinal enterocytes is regulated similarly to uptake from iron salts.     

Chromatographic determination of Fe chelated by ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid in commercial EDDHA/Fe3+ fertilizers

EDDHA/Fe3+ chelates are the most common fertilizers used to solve Fe chlorosis in established crops. Commercial products contain two regioisomers, ethylenediamine-N,N'-bis(o-hydroxyphenylacetic) acid (o,o-EDDHA)/Fe3+ and ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA)/Fe3+. Although several chromatographic methods exist for the determination of Fe3+ chelated by the o,o-EDDHA isomer, no method has been described for the quantification of Fe3+ chelated by o,p-EDDHA. In this work, factors that affect the behavior of o,p-EDDHA/Fe3+ in ion pair chromatography are reviewed: pH, ion pair reagent, and organic modifier. The best chromatographic performance was obtained with an aqueous mobile phase at pH 6.0 containing 35% acetonitrile and 5 mM tetrabutylammonium hydroxide under isocratic elution conditions. This method was applied to the quantification of commercial samples.     

Rates of cuticular penetration of chelated Fe(III): role of humidity, concentration, adjuvants, temperature, and type of chelate

Time courses of cuticular penetration of FeCl3 and Fe(III) complexes of citric acid, EDTA, EDDHA (Sequestrene 138Fe), imidodisuccinic acid (IDHA), and ligninsulfonic acid (Natrel) were studied using astomatous cuticular membranes (CMs) isolated from Populus x canescens leaves. At 100% relative humidity, the Fe(III) chelates disappeared exponentially with time from the surface of the CMs; that is, penetration was a first-order process that can be described using rate constants or half-times of penetration (t(1/2)). Half-times ranged from 20 to 30 h. At 90% humidity, penetration rates were insignificant with the exception of Natrel, for which t(1/2) amounted to 58 h. Rate constants were independent of temperature (15, 25, and 35 degrees C). Permeability decreased with increasing Fe chelate concentration (IDHA and EDTA). At 100% humidity, half-times measured with FeIDHA were 11 h (2 mmol L(-1)), 17 h (10 mmol L(-1)) and 36 h (20 mmol L(-1)), respectively. In the presence of FeEDTA, penetration of CaCl2 was slowed greatly. Half-times for penetration of CaCl2, which were 1.9 h in the absence of FeEDTA, rose to 3.12 h in the presence of an equimolar concentration of EDTA and 13.3 h when the FeEDTA concentration was doubled. Hence, Fe chelates reduced permeability of CMs to CaCl2 and to the Fe chelates themselves. It is suggested that Fe chelates reduced the size of aqueous pores. This view is supported by the fact that rate constants for calcium salts were about 5 times higher than for Fe chelates with the same molecular weights. Adding Tween 20 (5 g L(-1)) as a humectant did not increase permeability to FeIDHA at 90% humidity and below, while addition of glycine betaine did. Penetration of FeCl3 applied at 5 g L(-1) (pH 1.5) was not a first order process as rate constants decreased rapidly with time. Only 2% of the dose penetrated during the first 2 h and less than that in the subsequent 8 h. Recovery was only 70%. This was attributed to the formation of insoluble Fe hydroxide precipitates on CMs. These results explain why in the past foliar application of Fe compounds had limited success. Inorganic Fe salts are instable and phytotoxic because of low pH, while Fe chelates penetrate slowly and 100% humidity is required for significant penetration rates. Concentrations as low as reasonably possible should be used. These physical facts are expected to apply to stomatous leaf surfaces as well, but absolute rates probably depend on leaf age and plant species. High humidity in stagnant air layers may favor penetration rates across stomatous leaf surfaces when humidity in bulk air is below 100%.     

Interaction of Different Iron Chelates with an Alkaline and Calcareous Soil: A Complementary Methodology to Evaluate the Performance of Iron Compounds in the Correction of Iron Chlorosis

Abstract

A great number of studies have shown that the stability of iron chelates as a function of pH is not the unique parameter that must be considered in order to evaluate the potential effectiveness of Fe‐chelates to correct iron chlorosis in plants cultivated in alkaline and calcareous soils. In fact, other factors, such as soil sorption on soil components or the competition among Fe and other metallic cations for the chelating agent in soil solution, have a considerable influence on the capacity of iron chelates to maintain iron in soil solution available to plants. In this context, the aim of this work is to study the variation in concentration of the main iron chelates employed by farmers under field conditions—Fe‐EDDHA (HA), Fe‐EDDHMA (MA), Fe‐EDDHSA (SA), Fe‐EDDCHA (CA), Fe‐EDTA (EDTA), and Fe‐DTPA (DTPA)—in the soil solution of a calcareous soil over time. To this end, soil incubations were carried out using a soil:Fe solution ratio corresponding to soil field capacity, at a temperature of 23°C. The soil used in the experiments was a calcareous soil with a very low organic matter content. The variation in concentration of Fe and Fe‐chelates in soil solution over time were obtained by measuring the evolution in soil solution of both the concentration of total Fe (measured by AAS), and the concentration of the ortho‐ortho isomers for Fe‐EDDHA and analogs or chelated Fe for Fe‐EDTA and Fe‐DTPA (measured by HPLC). The following chelate samples were used: a HA standard prepared in the laboratory and samples of HA, MA, SA, CA, Fe‐EDTA, and Fe‐DTPA obtained from commercial formulations present in the market. The percentage of iron chelated as ortho‐ortho isomers for HAs was: HA standard (100%); HA (51.78%); MA (60.06%); SA (22.50%); and CA (27.28%). In the case of Fe‐EDTA and Fe‐DTPA the percentages of chelated iron were 96.09 and 99.12, respectively. Results show that it is possible to classify the potential effectiveness of the different types of iron chelates used in our experiments as a function of two practical approaches: (i) considering the variation of total iron in soil solution over time, MA is the best performing product, followed by HA, CA, SA, DTPA, EDTA, and ferrous sulfate in the order listed and (ii) considering the capacity of the different iron chelates to maintain the fraction of chelated iron (ortho‐ortho isomers for HA, MA, SA, and CA and total chelated iron for EDTA and DTPA) in soil solution, the order is: SA > CA > HA > MA > EDTA ≈ DTPA. This result, that is related to the nature of the chelate and does not depend on the degree of chelated Fe in the products, indicates that SA and CA might be very efficient products to correct iron chlorosis. Finally, our results also indicate the suitability of this soil incubation methodology to evaluate the potential efficiency of iron compounds to correct iron chlorosis.     

An assessment of EDTA as an extractant of organic-complexed and amorphous forms of Fe and Al in soils

EDTA solutions proposed as selective extractants of amorphous and organic forms of Fe and Al in soils and synthetic materials were tested. Extraction of Fe and Al from some soil samples continued at a decreasing rate beyond 120 days. For some soil samples and synthetic materials the amounts of Fe and Al extractable by EDTA (90 days) were markedly lower than those extractable by acid ammonium oxalate (2 h). Extraction of samples for 1 h with EDTA was shown to release amounts of Fe and Al far below those considered to be complexed with organic matter. The EDTA extraction procedures tested should not replace either acid ammonium oxalate for estimating amorphous forms of Fe and Al or pyrophosphate for estimating organic forms of Fe and Al in soils.     

Theoretical speciation of ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA) in agronomic conditions

The presence of ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA) as the second largest component in commercial EDDHA iron chelates has recently been demonstrated. Here is reported the speciation of o,p-EDDHA by the application of a novel methodology through the determination of the complexing capacity, protonation, and Ca(2+), Mg(2+), Cu(2+), and Fe(3+) stability constants. The pM values and species distribution in solution, hydroponic, and soil conditions were obtained. Due to the para position of one phenol group in o,p-EDDHA, the protonation constants and Ca and Mg stability constants have different values from those of o,o-EDDHA and p,p-EDDHA regioisomers. o,p-EDDHA/Fe(3+) stability constants are higher than those of EDTA/Fe(3+) but lower than those of o,o-EDDHA/Fe(3+). The sequence obtained for pFe is o,o-EDDHA/Fe(3+) >/= o,p-EDDHA/Fe(3+) > EDTA/Fe(3+). o,p-EDDHA/Fe(3+) can be used as an iron chelate in hydroponic conditions. Also, it can be used in soils with limited Cu availability.     

Interaction of iron chelates with several soil materials and with a soil standard

Frequently the effectiveness of iron (Fe) chelates is low because they can be retained or destroyed by soil materials. The high cost of these Fe fertilizers makes it necessary to study soil material reaction with Fe chelates. Commercial Fe chelates with EDTA, EDDHA, and EDDHMA as ligands and their standards, prepared in the laboratory, were shaken for one hour with various soil materials [amorphous Fe(III) oxide, acid peat, calcium (Ca)‐montmorillonite and calcium carbonate (CaCO₃)] and with a soil standard made in the laboratory. After agitation, the chelate‐soil mixtures were filtered and the micronutrients and chelated Fe that remained in solution were determined. Among the soil materials used, amorphous Fe(III) oxide and acid peat had the greatest affect on the amount of chelated Fe remaining in solution. The type of chelating agent was the next major factor that affected the availability of soluble Fe following reaction with the soil materials. Another factor was the commercial formulation of the Fe chelates. The chelates comprised of EDDHA or EDDHMA maintained the highest percentages of chelated Fe in solution after interaction with the solid phases, except for the acid peat. The last soil material, acid peat, retained more chelated Fe for the Fe chelates with EDDHA or EDDHMA than with EDTA as the chelating agent. The commercial Fe‐EDDHA chelates had greater losses of chelated Fe than their standard after interaction with all the solid phases. The commercial Fe‐EDDHA chelate (Sequestrene) and the commercial Fe‐EDDHMA chelate (Hampirón) solubilized the highest amount of copper (Cu) from soil standard. This was attributed to the presence of by‐products in the commercial formulations since the Fe‐EDDHA standard did not have Cu in solution after the interaction. Therefore, the commercial Fe chelate by‐products are able to form Cu‐complexes which could affect chelated Fe and its availability to plants.     

Fe Chelates for Remediation of Fe Chlorosis in Strategy I Plants

Abstract

Iron chlorosis is a mineral disorder due to low Fe in the soil solution and the impaired plant uptake mechanism. These effects increased with high pH and bicarbonate buffer. The solution to Fe chlorosis should be made by either improving the Fe uptake mechanism or increasing the amount of Fe in the soil solution. Among Fe fertilizers, only the most stable chelates (EDDHA and analogous) are able to maintain Fe in the soil solution and transport it to the plant root. In commercial products with the same chelating agent, the efficacy depends on the purity and the presence of subproducts with complexing activity, that can be determined by appropriate analytical methods such as HPLC. In commercial products declaring 6% as Fe‐EDDHA, purity varied from 0.5% to 3.5% before 1999, but in 2002 products ranging 3–5.4% chelated Fe are common in the Spanish market. Fe‐o,p‐EDDHA, as a synthesis by‐product with unknown efficacy, is present in all Fe‐EDDHA formulations. Commercial Fe‐EDDHMA products also contain methyl positional isomers. Fe‐EDDHSA synthesis produces condensation products with similar chelating capacity to the Fe‐EDDHSA monomer that can account for more than 50% of the chelated iron in the commercial products. Chelates with different molecules should be compared for their efficacy considering firstly their ability to maintain Fe in solution and secondly their capacity to release iron to the roots. Accepting the turnover hypothesis, their efficacy is also dependent thirdly on the ability of the chelating agent to form the chelate using native iron from the soil. The 1st and 3rd points are related to the chemical stability of the chelate, while plants make better use of iron from the less stable chelates. Plant response is the ultimate evaluation method to compare commercial products with the same chelating agent or different chelates.     

柑桔根系对缺铁的生理反应

柑桔在缺铁条件下,幼苗根系分泌H⁺和还原Fe³⁺的能力增加,与植株吸收铁素营养的能力相一致。摘除缺铁失绿的新叶和顶芽,抑制根系分泌H⁺和Fe³⁺还原物;但随着新叶的重新长出,根系分泌H⁺和Fe³⁺还原物的速率逐渐提高。说明缺铁失绿的组织能调控根系分泌H⁺和Fe³⁺还原物。在营养液中加入0.1nmol/L生长素(IAA),能解除因缺少失绿组织对根系分泌H～+产生的抑制作用。此外,在缺铁条件下,吸铁能力较强的酸橙根尖发生膨胀,有利于铁的接触吸收。     

Chemical properties and reactivity of manganese chelates and complexes in solution and soils

Commercial fertilizers containing synthetic manganese (Mn) chelates and complexes are currently used to alleviate Mn deficiency in crops. However, studies conducted on Mn sources in order to evaluate their behavior maintaining Mn soluble in nutrient solution and soil have not been done. In this work, representative commercial Mn fertilizers based on chelates and complexes were characterized and their chemical stability in solution and interaction with soils has been evaluated. Fertilizers studied were two ethylene diamine tetraacetic acid (EDTA) Mn chelates, one N‐(1,2‐dicarboxyethyl)‐D,L‐aspartic acid (IDHA) Mn chelate, two lignosulfonates, one carboxylate, one fulvate, one gluconate, and one heptagluconate‐based Mn complex. Characterization consisted of the determination of the soluble and chelated or complexed Mn, and the ligand identification by nuclear‐magnetic resonance (NMR). Stability study included batch experiments in Ca solution at different pH and three batch experiments with soil comparing with MnSO₄. Results indicate that most of the Mn fertilizers comply with the declared “soluble and chelated or complexed” metal content. At a usual pH range of calcareous soils (7.5–8.5), both chelates and complexes maintain more Mn in solution than MnSO₄ in the presence of Ca. Several factors affect the Mn remaining in solution after the interaction with the soil, especially, the soil‐to‐solution ratio. All chelates and complexes are better alternatives to the use of MnSO₄ in agronomical practices such as fertigation and soil application. Mn‐IDHA as chelate and Mn‐HGl or Mn‐Carb as complexes can be efficient, economical, and environmental friendly fertilizers for foliar application and hydroponic cultures. In soil application, Mn‐EDTA or Mn‐LS would be the best options. In this case, lignosulfonic acid represents a sustainable and low‐cost solution.     

铁氧化物影响土壤硝化作用动力学的作用机制

为探究铁氧化物对土壤硝化动力学的影响,以全铁含量低的酸性潮土(pH4.9)和中性潮土(pH7.2)为研究对象,通过7d的室内恒温(28℃)培养,研究了不同pH土壤在添加0(对照),0.5%,1%,3%,5%,10%(重量比)铁氧化物后的硝化动力学过程。结果表明:铁氧化物加入量超过3%,则改变中性潮土的硝化动力学过程由一级变为零级模型。不同含量铁氧化物加入后,酸性潮土的硝化过程均符合一级动力学模型。加铁处理的酸性潮土,其净矿化速率均显著高于不加铁处理。加铁量为10%处理的净矿化速率为4.12mg/(kg·d),是不加铁处理的7.82倍。随着铁氧化物加入量的增加,酸性潮土净硝化速率显著升高而中性潮土净硝化速率却显著下降。酸性潮土中铁氧化物加入量超过3%的处理,其净硝化速率极显著高于加铁量小于3%的处理。总之,铁氧化物的加入显著促进酸性潮土的净硝化速率,对中性潮土的净硝化速率却有显著抑制作用,并且加入量越大对2种土壤的作用效果越显著。3%的铁氧化物加入量是显著影响酸性潮土和中性潮土硝化作用的临界值。     

Effects of Fe compounds on nutrient uptake by plants grown in sand media with different pH

The effect of soil and foliar application of different iron (Fe) compounds (FeSO₄, Fe‐EDTA, Fe‐EDDS, and Fe‐EDDHA) on nutrient concentrations in lettuce (Lactuca sativa cv. Australian gelber) and ryegrass (Lolium perenne cv. Prego) was investigated in a greenhouse pot experiment using quartz sand as growth medium. Soil application was performed in both the acidic and alkaline pH range, and foliar application to plants grown in the alkaline sand only. Lettuce growth was depressed by Fe deficiency in the alkaline sand, whereas the treatments had no effect on ryegrass growth. Soil‐applied Fe compounds raised the Fe concentrations in lettuce. This was especially true for the Fe chelates, which also increased yields. Soil‐applied Fe compounds had no statistically significant effect on Fe concentrations in ryegrass. Concentrations of manganese (Mn) in lettuce were equally decreased by all soil‐applied chelates. In the alkaline sand, soil application of Fe‐EDDHA elevated copper (Cu) and depressed zinc (Zn) concentrations in lettuce. The chelates increased Zn concentration in ryegrass. Foliar application of Fe‐EDDS increased Fe concentrations in lettuce and in ryegrass most. Fe‐EDDHA depressed Mn and Zn concentrations in lettuce more than other Fe compounds, suggesting the existence of another mechanism, in addition to Fe, that transmits a corresponding signal from shoot to roots with an impact on uptake of micronutrients.     

Remediation of an electroplating contaminated soil by EDTA flushing: chromium release and soil dissolution

Purpose

Remediation of soils contaminated with Cr (as Cr(III) complexes/precipitates and/or Cr(VI) oxyanion) and cationic metals (Cu, Ni, Zn, and Pb) by ethylenediaminetetraacetate (EDTA) flushing has been challenging and rarely investigated. This study aimed to evaluate the efficiency of EDTA flushing for metal extraction of soil from an electroplating site, with a specific focus on chromium release and soil dissolution.

Materials and methods

Column flushing tests were performed on a sandy soil contaminated by electroplating activities in the field. Three EDTA concentrations (5, 10, and 20 mM) and flow interruptions were employed to investigate the operation of EDTA flushing.

Results and discussion

Results demonstrated that Cr, Cu, and Ni were continuously released along with dissolution of Fe, Al, Mg, and Mn throughout the entire flushing process (up to 600 pore volumes), whereas Zn and Pb removal primarily occurred in the first 50–200 pore volumes. By comparing the Cr and Fe release patterns, the observed Cr release by EDTA flushing possibly resulted from a combination of dissolution of Fe oxides, dissolution of metal–chromate precipitates, and ligand competition for the surface sites (substitution reaction). The latter two mechanisms appeared to be more influential at the early stage. It was also revealed that soil dissolution was predominant, and metal extraction became inefficient at the later stage of flushing, especially with the concentrated EDTA solution. On the other hand, when the flushing process was temporarily paused (i.e., flow interruptions), Cr, Cu, Ni, and Zn concentrations elevated, whereas Pb levels in the effluent decreased, indicating the significance of rate-limited metal exchange of newly formed metal–EDTA complexes.

Conclusions

In consideration of EDTA utilization efficiency and potential ecological risks, diluted EDTA solution is recommended for field applications.     

Nature of impurities in fertilizers containing EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+) chelates.

Iron chelates derived from ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA), ethylenediaminedi(o-hydroxy-p-methylphenylacetic) acid (EDDHMA), ethylenediaminedi(2-hydroxy-5-sulfophenylacetic) acid (EDDHSA), and ethylenediaminedi(5-carboxy-2-hydroxyphenylacetic) acid (EDDCHA) are remarkably efficient in correcting iron chlorosis in plants growing in alkaline soils. This work reports the determination of impurities in commercial samples of fertilizers containing EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+). The active components (EDDHMA/Fe(3+), EDDHSA/Fe(3+), and EDDCHA/Fe(3+)) were separated easily from other compounds present in the fertilizers by HPLC. Comparison of the retention times and the UV-visible spectra of the peaks obtained from commercial EDDHSA/Fe(3+) and EDDCHA/Fe(3+) samples with those of standard solutions showed that unreacted starting materials (p-hydroxybenzenesulfonic acid and p-hydroxybenzoic acid, respectively) were always present in the commercial products. 1D and 2D NMR experiments showed that commercial fertilizers based on EDDHMA/Fe(3+) contained impurities having structures tentatively assigned to iron chelates of two isomers of EDDHMA. These findings suggest that current production processes of iron chelates used in agriculture need to be improved.     

Iron treatment of lime‐induced chlorosis: Implications for chlorophyll,Fe2 +, Fe3 + and K+ in leaves 1

This study addressed some complementary aspects related to plant Fe nutrition. A field and a greenhouse experiment were conducted to monitor changes in chlorophyll, Fe³⁺, Fe²⁺, Ca²⁺ and K⁺ along with the progressive evolution of lime‐induced chlorosis, and following soil (Fe‐EDDHA, Fe‐EDTA, Fe‐DTPA, DTPA) and foliar (Fe‐EDDHA, FeSO₄, “Fe‐Metalosate") treatments, in a chlorosis‐susceptible ornamental plant, Hydrangea macrophylla, over a year's growing period. Though soil Fe‐EDDHA was the most effective compound in alleviating chlorosis symptoms, it became less so with time and was only partly effective as a foliar spray. Leaf analysis showed that as chlorosis intensified and chlorophyll content decreased, phenanthroline ‐ Fe (Fe²⁺) decreased with corresponding increases in total iron (Fe³⁺) and K⁺ concentrations. The reliability of these chlorosis‐indicators was confirmed as the reverse changes occurred upon chlorosis plant recovery.