Synthetic Chelators Research Articles

S,S]-EDDS/Fe: A new chelate for the environmentally sustainable correction of iron chlorosis in calcareous soil

Iron deficiency in crops is usually prevented and cured by the application of synthetic Fe chelates such as EDTA/Fe and the o,o-EDDHA/Fe. However their persistence in soil calls for the implementation of new alternatives that present less of a risk to the environment. This study therefore evaluated the biodegradable chelating agent [S,S]-EDDS as a new source for Fe fertilisation in calcareous soils in relation to its chemical reactivity. The suitability of [S,S]-EDDS/Fe as an Fe fertiliser in a calcareous soil was investigated and compared to the traditional synthetic chelates EDTA/Fe and o,o-EDDHA/Fe. Plant experiments with soybean (Glycine max), 57Fe isotopic labelling, and batch incubations were conducted in a calcareous soil. The Fe concentration of plants treated with [S,S]-EDDS/Fe was similar to those treated with EDTA/Fe. A similar Fe concentration to the o,o-EDDHA/Fe treatment was achieved using a double dose of [S,S]-EDDS/Fe. Despite the degradation of [S,S]-EDDS limiting the durability of [S,S]-EDDS/Fe in soil, the Fe bound to the degradation products may be a determining factor in improving Fe uptake and translocation to leaves in plants treated with [S,S]-EDDS/Fe compared to other Fe sources. Speciation studies by modelling and batch experiments also supported the lower reactivity of [S,S]-EDDS/Fe with calcium compared to that of EDTA/Fe, possibly contributing to the permanence of [S,S]-EDDS/Fe in the calcareous soil.This study demonstrated for the first time, that [S,S]-EDDS may be an environmentally sustainable alternative to traditional synthetic chelating agents such as EDTA or o,o-EDDHA for curing Fe chlorosis in susceptible plants in calcareous soil.

Boron: Functions and Approaches to Enhance Its Availability in Plants for Sustainable Agriculture.

Boron (B) is an essential trace element required for the physiological functioning of higher plants. B deficiency is considered as a nutritional disorder that adversely affects the metabolism and growth of plants. B is involved in the structural and functional integrity of the cell wall and membranes, ion fluxes (H+, K+, PO43−, Rb+, Ca2+) across the membranes, cell division and elongation, nitrogen and carbohydrate metabolism, sugar transport, cytoskeletal proteins, and plasmalemma-bound enzymes, nucleic acid, indoleacetic acid, polyamines, ascorbic acid, and phenol metabolism and transport. This review critically examines the functions of B in plants, deficiency symptoms, and the mechanism of B uptake and transport under limited B conditions. B deficiency can be mitigated by inorganic fertilizer supplementation, but the deleterious impact of frequent fertilizer application disrupts soil fertility and creates environmental pollution. Considering this, we have summarized the available information regarding alternative approaches, such as root structural modification, grafting, application of biostimulators (mycorrhizal fungi (MF) and rhizobacteria), and nanotechnology, that can be effectively utilized for B acquisition, leading to resource conservation. Additionally, we have discussed several new aspects, such as the combination of grafting or MF with nanotechnology, combined inoculation of arbuscular MF and rhizobacteria, melatonin application, and the use of natural and synthetic chelators, that possibly play a role in B uptake and translocation under B stress conditions.

The labile iron pool attenuates peroxynitrite-dependent damage and can no longer be considered solely a pro-oxidative cellular iron source

The ubiquitous cellular labile iron pool (LIP) is often associated with the production of the highly reactive hydroxyl radical, which forms through a redox reaction with hydrogen peroxide. Peroxynitrite is a biologically relevant peroxide produced by the recombination of nitric oxide and superoxide. It is a strong oxidant that may be involved in multiple pathological conditions, but whether and how it interacts with the LIP are unclear. Here, using fluorescence spectroscopy, we investigated the interaction between the LIP and peroxynitrite by monitoring peroxynitrite-dependent accumulation of nitrosated and oxidized fluorescent intracellular indicators. We found that, in murine macrophages, removal of the LIP with membrane-permeable iron chelators sustainably accelerates the peroxynitrite-dependent oxidation and nitrosation of these indicators. These observations could not be reproduced in cell-free assays, indicating that the chelator-enhancing effect on peroxynitrite-dependent modifications of the indicators depended on cell constituents, presumably including LIP, that react with these chelators. Moreover, neither free nor ferrous-complexed chelators stimulated intracellular or extracellular oxidative and nitrosative chemistries. On the basis of these results, LIP appears to be a relevant and competitive cellular target of peroxynitrite or its derived oxidants, and thereby it reduces oxidative processes, an observation that may change the conventional notion that the LIP is simply a cellular source of pro-oxidant iron.

Structural Basis for the Catalytic Mechanism of Ethylenediamine- N, N'-disuccinic Acid Lyase, a Carbon-Nitrogen Bond-Forming Enzyme with a Broad Substrate Scope.

The natural aminocarboxylic acid product ethylenediamine-N,N′-disuccinic acid [(S,S)-EDDS] is able to form a stable complex with metal ions, making it an attractive biodegradable alternative for the synthetic metal chelator ethylenediaminetetraacetic acid (EDTA), which is currently used on a large scale in numerous applications. Previous studies have demonstrated that biodegradation of (S,S)-EDDS may be initiated by an EDDS lyase, converting (S,S)-EDDS via the intermediate N-(2-aminoethyl)aspartic acid (AEAA) into ethylenediamine and two molecules of fumarate. However, current knowledge of this enzyme is limited because of the absence of structural data. Here, we describe the identification and characterization of an EDDS lyase from Chelativorans sp. BNC1, which has a broad substrate scope, accepting various mono- and diamines for addition to fumarate. We report crystal structures of the enzyme in an unliganded state and in complex with formate, succinate, fumarate, AEAA, and (S,S)-EDDS. The structures reveal a tertiary and quaternary fold that is characteristic of the aspartase/fumarase superfamily and support a mechanism that involves general base-catalyzed, sequential two-step deamination of (S,S)-EDDS. This work broadens our understanding of mechanistic diversity within the aspartase/fumarase superfamily and will aid in the optimization of EDDS lyase for asymmetric synthesis of valuable (metal-chelating) aminocarboxylic acids.

Zinc fertilizers influence greenhouse gas emissions and nitrifying and denitrifying communities in a non-irrigated arable cropland

Fertilization with micronutrients (e.g., zinc, Zn) is essential in order to overcome the global nutritional problems associated with human micronutrient deficiencies. However, little is known about the effect of micronutrient fertilizers and their interaction with nitrogen (N) on greenhouse gas (GHG) emissions and soil microbial processes involved in nitrous oxide (N2O) fluxes. In this context, a one-year field experiment was carried out using a winter wheat (Triticum aestivum L.) crop in Central Spain. Winter wheat was treated with different Zn sources (Zn-sulphate, Zn-lignosulphonate, Zn with a mixture of synthetic chelating compounds DTPA-HEDTA-EDTA and Zn-humic/fulvic acids) and N rates (0, 120 and 180 kg N ha−1). Zn sources were applied at 10 kg Zn ha−1 for Zn-sulphate and 0.36 kg Zn ha−1 for the rest of treatments. Nitrous oxide, methane (CH4) and respiration fluxes were measured (two-three times per week during the first month after each fertilization and thereafter with decreasing frequency), as were the total abundances of soil Bacteria and Archaea, ammonia-oxidizing Bacteria and Archaea, and denitrifying bacteria. The DTPA-HEDTA-EDTA reduced cumulative N2O losses by 21.4% and respiration fluxes by 24.4% from those of the no Zn application. The chelating of metal co-factors (mainly copper, Cu) of the enzymes involved in the nitrification and denitrification steps was the probable mechanism for the reduction of N2O emissions as bacterial amoA, nirK, nirS and norB gene abundances, as well as the extractable Cu content, decreased in this treatment. Unexpectedly, the DTPA-HEDTA-EDTA increased the copy number of nosZ by 31.2% over that of the no Zn application. The Zn applied together with the humic/fulvic acids mixture caused significant increases of total bacterial abundance and nitrifier and denitrifier communities, particularly the norB gene, thereby leading to the highest N2O emissions. The optimum N rate was 120 kg N ha−1 since it resulted in the lowest yield-scaled N2O losses and N surplus. The application of synthetic Zn chelates can be recommended as a win-win mitigation and adaptation strategy aimed at reducing yield-scaled GHG emissions and at the enhancement of Zn biofortification.

Design, solid-phase synthesis and evaluation of enterobactin analogs for iron delivery into the human pathogen Campylobacter jejuni

The human enteropathogen Campylobacter jejuni, like many bacteria, employs siderophores such as enterobactin for cellular uptake of ferric iron. This transport process has been shown to be essential for virulence and presents an attractive opportunity for further study of the permissiveness of this pathway to small-molecule intervention and as inspiration for the development of synthetic carriers that may effectively transport cargo into Gram-negative bacteria. In this work, we have developed a facile and robust microscale assay to measure growth recovery of C. jejuni NCTC 11168 in liquid culture as a result of ferric iron uptake. In parallel, we have established the solid-phase synthesis of catecholamide compounds modeled on enterobactin fragments. Applying these methodological developments, we show that small synthetic iron chelators of minimal dimensions provide ferric iron to C. jejuni with equal or greater efficiency than enterobactin.

Evaluation of copper toxicity using site specific algae and water chemistry: Field validation of laboratory bioassays

Studies of metal toxicity to microalgae have predominantly been conducted using single non-target algae species and without due regard for the chemistry of the treated waters, leading to ineffective or excessive algaecide treatments. In this study, indigenous multi-algal species (Scenedesmus quadricauda, and Scenedesmus subspicatus and Oscillatoria agardhii) were used in laboratory toxicity bioassays under simulated field water chemistry (pH = 7.2, hardness = 196 mg L−1 as CaCO3, and alkalinity = 222 mg L−1 as CaCO3) to determine the optimum copper sulfate treatment dose to control algae growth in an irrigation canal. Toxicity bioassays were conducted using copper sulfate in chelated (with EDTA) and non-chelated (without EDTA) forms to assess the influence of the use of synthetic chelators in toxicity studies. Also, copper toxicity to the indigenous algae species was measured in the non-modified EPA test medium (pH = 7.5, hardness = 92 mg L−1 as CaCO3, alkalinity = 10 mg L−1 as CaCO3 and EDTA= 300 µg L−1) to assess the impact of the water chemistry on algae inhibitory algal dosages. Under simulated water chemistry conditions, lower toxicity was measured in the test flasks with the chelated form of copper (96 h- EC50= 386.67 µg L−1 as Cu) as compared to those with the non-chelated metal (96 h-EC50= 217.17 µg L−1 as Cu). In addition, higher copper toxicity was measured in the test flasks prepared with the non-modified EPA medium using chelated copper (96 h-EC50 = 65.93 µg L−1 as Cu) as compared to their analogous microcosms with modified water chemistry (96 h-EC50= 386.67 µg L−1 as Cu), the increased water hardness and alkalinity in the latter case contributing to the decrease of the metal bioavailability. Results from laboratory experiments showed good correlation with copper dosages used in a small scale field testing to control algae growth, increasing confidence in laboratory bioassays.

Rapid evolution of a bacterial iron acquisition system.

Under iron limitation, bacteria scavenge ferric (Fe3+ ) iron bound to siderophores or other chelates from the environment to fulfill their nutritional requirement. In gram-negative bacteria, the siderophore uptake system prototype consists of an outer membrane transporter, a periplasmic binding protein and a cytoplasmic membrane transporter, each specific for a single ferric siderophore or siderophore family. Here, we show that spontaneous single gain-of-function missense mutations in outer membrane transporter genes of Bradyrhizobium japonicum were sufficient to confer on cells the ability to use synthetic or natural iron siderophores, suggesting that selectivity is limited primarily to the outer membrane and can be readily modified. Moreover, growth on natural or synthetic chelators required the cytoplasmic membrane ferrous (Fe2+ ) iron transporter FeoB, suggesting that iron is both dissociated from the chelate and reduced to the ferrous form within the periplasm prior to cytoplasmic entry. The data suggest rapid adaptation to environmental iron by facile mutation of selective outer membrane transporter genes and by non-selective uptake components that do not require mutation to accommodate new iron sources.

Binding of proton and iron to lignite humic acid size-fractions in aqueous matrix

The bioavailability of trivalent iron (Fe3+) to plants can be enhanced using fertilizer solutions containing humic acids (HA) as manifested from the increased crop yield at an iron stress conditions. The lignite-derived HA (HAlignite) facilitates higher diffusion of Fe3+ between the soil layers as attributable to more number of reactive sites in the assemblage compared to those from other origins. In the current work, the proton-binding of HAlignite size-fractions (5–10, 10–30, 30–100, and >100 kDa), as segmented based on the molecular weight distribution, and their complexation with Fe3+ have been studied at varying pH ranging from low to high. The protonation or formation of Fe3+-complexes exhibited a comparable pattern despite the differences in the conformational distribution of HAlignite size-fractions. The protonation behavior specified that the behavior of HAlignite size-fractions has similarity with that of a dibasic acid. The results are interpreted using reactive structural units (RSU) concept to show that the carboxyl and phenolic-hydroxyl groups in the HAlignite size-fractions simultaneously available as the Fe3+-binding sites. The stability constants for larger MW fractions of HAlignite (>100 kDa) was the lowest, as attributed to the increased aggregation rate in an aqueous matrix. The trend in conditional stability constants of HAlignite-size fractions and other Fe-chelators point to a better Fe-binding capability of HAlignite (30–100 kDa) size-fraction than the biodegradable alternatives (GLDA, HIDS, EDDS, IDSA, or NTA), while the Fe-interaction was stronger with classical synthetic chelators (EDTA, DTPA, or EDDHA).

Effects of organic ligands and background electrolytes on barite dissolution

Barite dissolution rates and features were investigated under conditions that combine a variety of organic ligands with different background electrolyte solutions. The organic ligands included low molecular weight organic compounds (LMWO) that can be produced by halophilic bacteria and are common in natural environments, as well as synthetic chelators that were previously studied in barite dissolution. Background electrolyte solutions included deionized water, 0.72 M NaCl and 2 M NaCl solutions designed to simulate freshwater, seawater, and brine fluids, respectively. Barite dissolution rates and corresponding rate constants normalized for saturation states were calculated for most experiments. Equal or lower rates and rate constants for pure LMWO relative to controls at all background electrolyte concentrations and pH values indicated that LMWO do not promote barite dissolution. Synthetic chelators showed higher rates and rate constants at pH 10 at static conditions than controls, indicating enhanced barite dissolution. Distinctive etch pit morphologies on the barite (0 0 1) face were observed in the presence of synthetic chelators, suggesting a direct contact dissolution mechanism by synthetic chelators. The effect of synthetic chelators on barite dissolution was significantly reduced in the presence of 2 M NaCl and/or at pH 6.5 due to salting out effects. Under hypersaline conditions, barite dissolution rates and rate constants by bacterial activities were up to four times higher than those of synthetic chelators. The wide range of conditions studied in this work provides insights into prediction of barite dissolution behavior in various natural environments as well as in industrial treatment procedures.

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N′,N′-tetraacetic acid (TMDTA) was investigated over the pH range 5.50–8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4–5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2− and FeII(H)L− to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2−. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation rates at higher pH. Finally, this work demonstrates that the rate of FeII oxidation is very sensitive to the identity and structure of the polyaminocarboxylate chelating agent, which has implications for any metal or organic chemical that reacts either directly or indirectly with iron.

Industrial Applications of Selected JFS Articles

Industrial Applications of Selected <i>JFS</i> Articles

Azotochelin and N-dihydroxy-N,N’-diisopropylhexanediamide as Fe sources to cucumber plants in hydroponic cultures

Environmental concerns related to the use of synthetic iron chelates, usually non-biodegradable, for overcoming iron chlorosis motivates the search for alternative compounds. Thus, the main aim of this work was to evaluate siderophore, azotochelin, and a siderophore mimic, N-dihydroxy-N,N’-diisopropylhexanediamide (DPH) as potential sources of iron to cucumber plants grown in hydroponic cultures. The behavior of the iron chelates of azotochelin and DPH, as a substrate of ferric chelate reductase (FCR) and the ability as iron suppliers for chlorotic plants was studied and compared with o,o-EDDHA/Fe3+ and EDTA/Fe3+ chelates, traditionally used for this purpose. The rate of reduction of DPH/Fe3+, by FCR, was comparable to o,o-EDDHA/Fe3+ but lesser than the obtained for EDTA/Fe+3. The rate of reduction for azotochelin/Fe3+ was not possible to determine. Both azotochelin/Fe3+ and DPH/Fe3+ chelates were effective in supplying iron to cucumber plants. After 7 and 21 days, all the plants treated with the iron chelates (10 µM, Fe) of DPH and azotochelin showed significantly higher SPAD index, leaf dry weight and leaf Fe concentration than the control plants (2µM, Fe). In conclusion, azotochelin/Fe3+ and DPH/Fe3+ can be considered as iron sources for cucumber plants when growing in hydroponic culture.

Identifying the functional groups and the influence of synthetic chelators on Cd availability and microbial biomass carbon in Cd-contaminated soil

ABSTRACTSynthetic chelators play an important role in boosting the microbial biomass carbon (MBC), dissolved organic carbon (DOC), and heavy metal solubility in a contaminated soil toward a sustainability of environment for agricultural crops. Castor plant was grown under different levels of Cd contaminated soil (−Cd and +Cd) following adding three chelating agents, ethylenediaminetetraacetic acid (H4EDTA), nitriloacetic acid (H3 NTA), and NH4 citrate (ammonium citrate) to the soil at rates of 10, 15, and 25 mmol in 5 kg of soil per pot. The highest bioavailable Cd concentrations in soil and castor plant were obtained from NH4 citrate and H4EDTA treatments in the contaminated soil. Fourier transform infrared (FTIR) analysis showed that NH4 citrate was the most effective chelator in Cd-contaminated soil. MBC and DOC contents were significantly increased and reached at 81.98–80.37 and 1.96–1.90 mg kg−1 respectively, in the (H3 NTA) and NH4 citrate treatments in Cd-contaminated soil. Further research is needed to investigate the use of chelators in the phytoextraction of Cd-contaminated soils under field conditions and whether it may be beneficial in accelerating the phytoextraction of Cd through hyperaccumulating plants.

Hepatoprotective potential of the methanolic extract of Colocasia esculenta on iron overload induced mice

Over deposition of iron in the body lead to oxidative damage in cells and organs of the body which is characterized as iron overload disease. Present study was aimed to measure the remedial effect and Colocasia esculenta under iron overload diseased conditions. C. esculenta is a tropical plant belonging to Araceae family highly rich in alkaloids, flavonoids, saponins, and tannins. In vitro assays, C. esculenta methanolic extract (CEME) proved iron chelation and reducing power in dose dependent manner. Thirty-six mice were divided into six groups out of that one was normal group which received water and remaining five represented iron overloaded conditions induced by iron sucrose injection. The diseased groups received oral doses of CEME (50, 100, and 200 mg/kg b.w.), desirox group that received doses of synthetic chelator desirox (20 mg/kg b.w.) and the negative control group that were provided with normal saline water ad libitum. Several biochemical markers of hepatic damage characterized in liver and serum were studied. Tissue histopathological study was done to understand the morphological changes. The reducing power and iron chelation capacity of CEME was studied and found that CEME (200 mg/kg b.w.) significantly normalized the levels of alanine aminotransferase and aspartate aminotransferase by 63.88% and 22.46%, respectively. CEME (200 mg/kg b.w.) was shown to alleviate the reduced levels of superoxide dismutase, catalase, glutathione-S-transferase, and nonenzymatic-reduced glutathione by 15.59%, 28.78%, 37.56%, and 35.56%, respectively. These findings suggest that, the protective effect of CEME against iron-overloaded-induced liver toxicity as evidenced by biochemical and histopathological studies.

Application of manures to mitigate the harmful effects of electrokinetic remediation of heavy metals on soil microbial properties in polluted soils.

Ethylenediaminetetraacetic acid (EDTA) used with electrokinetic (EK) to remediate heavy metal-polluted soils is a toxic chelate for soil microorganisms. Therefore, this study aimed to evaluate the effects of alternative organic chelates to EDTA on improving the microbial properties of a heavy metal-polluted soil subjected to EK. Cow manure extract (CME), poultry manure extract (PME) and EDTA were applied to a lead (Pb) and zinc (Zn)-polluted calcareous soil which were subjected to two electric intensities (1.1 and 3.3v/cm). Soil carbon pools, microbial activity, microbial abundance (e.g., fungal, actinomycetes and bacterial abundances) and diethylenetriaminepentaacetic acid (DTPA)-extractable Pb and Zn (available forms) were assessed in both cathodic and anodic soils. Applying the EK to soil decreased all the microbial variables in the cathodic and anodic soils in the absence or presence of chelates. Both CME and PME applied with two electric intensities decreased the negative effect of EK on soil microbial variables. The lowest values of soil microbial variables were observed when EK was combined with EDTA. The following order was observed in values of soil microbial variables after treating with EK and chelates: EK+CME or EK+PME>EK>EK+EDTA. The CME and PME could increase the concentrations of available Pb and Zn, although the increase was less than that of EDTA. Overall, despite increasing soil available Pb and Zn, the combination of EK with manures (CME or PME) mitigated the negative effects of using EK on soil microbial properties. This study suggested that the synthetic chelates such as EDTA could be replaced with manures to alleviate the environmental risks of EK application.

Response of soybean plants to the application of synthetic and biodegradable Fe chelates and Fe complexes

The growing concern over the environmental risk of synthetic chelate application promotes the search for alternatives in Fe fertilization, such as biodegradable chelating agents and natural complexing agents. In this work, plant responses to the application of several Fe treatments (chelates and complexes) was analyzed to study their potential use in Fe fertilization under calcareous conditions. Thus, the root ferric chelate reductase (FCR) activity of soybean (Glycine max cv. Klaxon) plants was determined, and the effectiveness of the Fe chelates and complexes assessed in a pot experiment, by SPAD and fluorescence induction measurements, and the determination of Fe distribution in plant and soil. Additionally, 57Fe Mössbauer spectroscopy was conducted to identify the Fe forms present in the soybean roots. The highest FCR activity was observed for the chelates EDDS/Fe3+ and IDHA/Fe3+; while no activity was observed when using complexes as Fe substrates. In contrast to the FCR data, the pot experiment confirmed that the o,oEDDHA/Fe3+ is the most effective treatment, and the complexes LS/Fe3+ and GA/Fe3+ are able to alleviate Fe chlorosis, also indicated by SPAD data and the maximal quantum efficiency of photosystem II reaction centers as vitality parameters, and the enhanced plant uptake of Fe from natural sources.

Cadmium removal from Cd-contaminated soils using some natural and synthetic chelates for enhancing phytoextraction

ABSTRACTThe influence of a natural (citric acid) and two synthetic chelates (HEDTA, EGTA) on Cd phytoextraction with radish was studied. The experiment was conducted with Cd treatments including 0 (control), 5, 20, 60 and 100 mg Cd kg−1 soil. When plants were fully developed, the designated HEDTA, EGTA and citric acid were applied to establish experimental treatments. Ten days after chelate applications, soil and plant samples were taken. Results indicated that synthetic chelates can considerably increase Cd concentration in soil solution compared with citric acid. Among the applied chelates, HEDTA provided more significant influences on soil solution. Cadmium concentration in both shoots and roots of radish was increased due to enhancing influence of chelate applications on Cd concentration in soil solution. Cadmium concentration in radish shoots was more than that of roots. This can be attributed to higher bioavailability and solubility of Cd in soil solution. In all treatments which received HEDTA, the cadmium concentration in both shoots and roots of radish was increased more than that of other applied chelates. Although HEDTA is more efficient in phytoextracting Cd than other chelates, due to durability of synthetic chelates toxic effects on soils, we recommend using larger amounts of light acids.

N,N′-Dihydroxy-N,N′-diisopropylhexanediamide, a siderophore analogue, as a possible iron chelating agent for hydroponic conditions: metal equilibrium studies

Synthetic iron chelates are the most efficient iron fertilizers. The stability in solution of the iron chelates in the presence of other metal cations that may compete with iron for the chelating agent in nutrient solutions is crucial for its effectiveness in supplying iron to plants. In this work, the chelating properties of N,N-dihydroxy-N,N′-diisopropylhexanediamide (DPH), a biological model of the natural siderophore rhodotorulic acid, were evaluated in order to assess its potentialities for being used, as an iron chelate, in hydroponic cultures. For this purpose, the complexation for the metals [Ca(II), Cu(II), Mg(II), Mn(II) or Zn(II)]–DPH–OH systems has been studied using pH potentiometry and the overall stability constants have been determined for the first time. For all M–DPH–OH systems, MHL and ML species were identified. For [Cu(II), Mn(II) or Zn(II)]–DPH–OH systems, the M2L3 species was detected, whereas formation of ML(OH) species was found in the [Ca(II) or Mg(II)]–DPH–OH systems. Finally, the chemical stability of iron chelated with DPH in hydroponic conditions was assessed by computer chemical simulations and compared with the one predicted when iron is chelated with ethylenediamine-N,N′-bis(o-hydroxyphenyl)acetic acid (o,o-EDDHA) in similar conditions.

Ameliorative Effect of Chelating Agents on Photosynthetic Attributes of Cd Stressed Sunflower

Excessive input of heavy metals in water reservoir and cultivated land primarily affects the growth and yield of crops. The aim of this work was to study the mechanism of Cd toxicity and damage to photosynthetic pigments and their efficiency and the potential of natural (OA) and synthetic chelators (EDTA) in assisting the phytoextractor sunflower plant. The pot experiment was laid out in a complete randomized way for Cd, chelators and hybrids at seedling, vegetative and reproductive stages with three replications. Cd affects the gas exchange parameters directly or indirectly by affecting the light and dark reactions, while indirect effect includes inhibition of chlorophyll and carotenoids biosynthesis and degradation and alteration in Chl a/b ratio. Among two chelators, natural chelator OA found to be very supportive in ameliorating the Cd tocixity by phytoextractor in assistance to sunflower hybrid Hysun-33.