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.     

Efficacy of Fe(o,o-EDDHA) and Fe(o,p-EDDHA) isomers in supplying Fe to strategy I plants differs in nutrient solution and calcareous soil

The FeEDDHA [iron(3+) ethylenediamine di(o-hydroxyphenylacetic) acid] is one of the most efficient iron chelates employed in the correction of iron clorosis in calcareous soils. FeEDDHA presents different positional isomers: the ortho-ortho (o,o), the ortho-para (o,p), and the para-para (p,p). Of these isomers, the p,p cannot chelate Fe in soil solution in a wide range of pH values, while both o,o and o,p can. The objective of this work was to compare the efficiency of both isomers (o,o and o,p) to provide Fe to two Strategy I plants (tomato and peach) in nutrient solution (pH approximately 6.0), as well as in calcareous soil (pH approximately 8.4; CALCIXEREPT). For this, chelates of both o,o-EDDHA and o,p-EDDHA with 57Fe (a nonradioactive isotope of Fe) were used, where the 57Fe acts as a tracer. The results obtained showed that the o,o isomer is capable of providing sufficient Fe to plants in both nutrient solution and calcareous soil. However, the o,p isomer is capable of providing sufficient Fe to plants in nutrient solution but not in calcareous soil.     

Stability in solution and reactivity with soils and soil components of iron and zinc complexes

Naturally derived complexes with the ability to complex (unidentate) or chelate (polydentate) metals are a cheaper alternative to synthetic chelates to correct micronutrient deficiencies, but despite their widespread use there is a lack of knowledge on their agronomic performance. The aim of this paper was to evaluate the stability of iron (Fe) and zinc (Zn) lignosulfonate, gluconate, amino acid, and humate complexes in solution over time and at different pH values. Also, their stability in a concentrated nutrient solution and their reactivity with soils and soil components was evaluated. In our experimental conditions, all the complexes (except Fe amino acid) remained stable in solution for an extended period of time. All Zn complexes and the Fe lignosulfonate were stable in solution up to pH 7.0–7.5, while Fe gluconate only maintained 20%–40% of the iron in solution in the pH range 5–11 and Fe amino acid and humate complexes barely maintained small concentrations of Fe in solution above pH 3. Most of the complexes maintained Fe and Zn in concentrated nutrient solutions for irrigation systems, but Fe amino acid only maintained around 70% of the iron added. In general, the interactions of complexes with soils and soil components produced a high retention. The interaction of Fe lignosulfonate with peat, illite, and ferrihydrite, and Fe gluconate with peat and illite resulted in significant amounts of Fe to remain in solution, while for the Fe amino acid and humate the Fe remaining in solution was low. All Zn complexes were highly retained in an acidic peat, illite, and montmorillonite clays and soils, while no retention was observed on ferrihydrite. In conclusion, the stability of complexes in different conditions is related to the percentage of complexed element in the products. While complexes can be used to maintain micronutrients in solution in aqueous media (foliar and fertigation), their application to soil should be considered as a measure to increase metal availabilities but not their solubility.     

Analysis of iron chelates in commercial iron fertilizers by gel chromatography

A gel chromatographic method for the quality control of iron chelate fertilizers is described. The iron chelates are separated on a column of Sephadex G-10 and the eluates are analysed for iron. Using a sample quantity of 25 mg in a volume of 5 ml water and eluting with 0.15 M soidum chloride solution, a separation was achieved of commercial products of Fe-EDDHA or Fe-EDDHMA. The chromatographic analysis of Fe-EDTA or Fe-DTPA calls for a better resolution. This was obtained by decreasing the sample quantity and eluting with 0.035 M calcium chloride solution of pH 7.0. In this way it is possible to eliminate the interference of iron chelates of moderate stability which can be present in commercial products containing Fe-EDTA or Fe-DTPA.     

Kinetic behavior of Fe(o,o-EDDHA)-humic substance mixtures in several soil components and in calcareous soils

Ferric ethylenediamine- N, N'-bis-(o-hydroxyphenylacetic)acid chelate (Fe(o, o-EDDHA)) is one of the most effective Fe fertilizers in calcareous soils. However, humic substances are occasionally combined with iron chelates in drip irrigation systems in order to lower costs. The reactivity of iron chelate-humic substance mixtures in several soil components and in calcareous soils was investigated through interaction tests, and their behavior was compared to the application of iron chelates and humic substances separately. Two commercial humic substances and two Fe(o, o-EDDHA) chelates (one synthesized in the laboratory and one commercial) were used to prepare iron chelate-humic substance mixtures at 50% (w/w). Various soil components (calcium carbonate, gibbsite, amorphous iron oxide, hematite, tenorite, zincite, amorphous Mn oxide, and peat) and three calcareous soils were shaken for 15 days with the mixtures and with iron chelate and humic substance solutions. The kinetic behavior of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) (Fe bonded to (o,p-EDDHA) and other polycondensated ligands) and of the different nutrients solubilized after the interaction assay was determined. The results showed that the mixtures did not significantly reduce the retention of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) in the soil components and the calcareous soils compared to the iron chelate solutions, but they did produce changes in the retention rate. Moreover, the competition between humic substances and synthetic chelating agents for complexing metal cations limited the effectiveness of the mixtures to mobilize nutrients from the substrates. The presence of Fe(o, p-EDDHA) and other byproducts in the commercial iron chelate had an important effect on the evolution of Fe(o, o-EDDHA) and the nutrient solubilization process.     

Sorption of humic acid on Fe oxides,bacteria, and Fe oxide-bacteria composites

Purpose

Sorption of humic substances on other soil components plays an important role in controlling their function and fate in soil. Sorption of humic substances by individual soil components has been studied extensively. However, few studies reported the sorption characteristic of humic substances on composites of soil components. This study aimed to investigate the sorption characteristics of humic acid on Fe oxide-bacteria composites and improve the understanding on the interaction among humic substance Fe oxide bacteria in soil.

Materials and methods

Humic acid was purchased from Sigma-Aldrich and was purified. Hematite and ferrihydrite were synthesized in the lab. Bacillus subtilis and Pseudomonas putida were cultivated in Luria-Broth medium and harvested at stationary growth phase. Batch sorption experiments were carried out at pH 5.0. Various amounts of humic acid were mixed with 20 mg of Fe oxide, bacteria, or Fe oxide-bacteria composite (oxide to bacteria of 1:1) in 10 mL of KCl (0.02 mol L^?1) to construct sorption isotherms. The effects of phosphate concentration and addition order among humic acid, Fe oxide, bacteria on the sorption of humic acid were also studied. The sorption of humic acid was calculated by the difference between the amount of humic acid added initially and that remained in the supernatant.

Results and discussion

The maximum sorption of humic acid on hematite, ferrihydrite, B. subtilis and P. putida was 73.2, 153.5, 69.1, and 56.7 mg C g^?1, respectively. The maximum sorption of humic acid on examined Fe oxide-bacteria composite was 28.2–57.2 % less than the predicted values, implying that the sorption of humic acid was reduced by the interaction between Fe oxides and bacteria. The presence of phosphate exerted negligible influence on the sorption of humic acid on bacteria while it inhibited the sorption of humic acid on Fe oxides. On Fe oxide-bacteria composites, inhibiting influences followed by promoting or weak inhibiting effects of phosphate with increasing concentration on the sorption of humic acid were found.

Conclusions

The interaction between Fe oxides and bacteria reduced the sorption of humic acid; moreover, the reduction was greater by the interaction of bacteria with ferrihydrite than that with hematite. Phosphate exerted negligible and inhibiting influence on the sorption of humic acid by bacteria and Fe oxides, respectively. On Fe oxide-bacteria composites, humic acid sorption was initially inhibited and then promoted or weakly inhibited by phosphate with increasing concentration.     

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.     

Effect of Fe-Glycine Aminochelate on Pod Quality and Iron Concentrations of Bean (Phaseolus vulgaris L.) Under Lime Soil Conditions

Iron (Fe) has very low solubility and plant availability in calcareous soils, and this generally results in restricted plant production and low quality. During last decades, various commercial chelated fertilizers have been used in agricultural systems to meet iron requirements of crops. However, despite extensive application of these commercial chelate fertilizers, there is real doubt and high concerns regarding many aspects of their action, dynamics, efficiency, and safety in plant-soil–environment systems. In the present study, growth and quality of green bean plants (Phaseolus vulgaris L.) were evaluated under foliar and soil applications of Fe-glycine chelate (iron glycine aminochelate) and commercial Fe-EDDHA chelate in a lime soil. The results showed that morphophysiological parameters were improved by the application of Fe-glycine and Fe-EDDHA treatments. Foliar application of Fe-glycine has significantly improved leaf area and Soil-Plant Analyses Development (SPAD) values compared to control and Fe-EDDHA treatments. Pod yield, shoot (but not root) dry weight, and iron concentrations in leaves and pods (but not in root) were significantly higher when plants were treated by Fe-glycine rather than Fe-EDDHA in both soil and foliar applications. Vitamin C and protein contents were significantly improved and phenolic compounds were reduced by foliar application of Fe-glycine and soil application of Fe-EDDHA. The results indicate that foliar application of Fe-glycine can significantly increase Fe concentrations and quality of beans under lime soils with restricted iron availability.     

Fe uptake from meso and D,L-racemic Fe(o,o-EDDHA) isomers by strategy I and II plants

One of the most efficient fertilizers to correct Fe deficiency in calcareous soils and waters with high bicarbonate content is based on ferric ethylenediamine-N,N'-bis(o-hydroxyphenylacetic) acid [Fe(o,o-EDDHA)]. Fe(o,o-EDDHA) forms two groups of geometric isomers known as meso and D,L-racemic. To determine the Fe uptake from meso and D,L-racemic Fe(o,o-EDDHA), four iron-efficient plants, two plants representative of strategy I (tomato and pepper) and two plants representative of strategy II (wheat and oats), were grown in hydroponic culture. Results indicated that strategy II plants took up iron from both Fe(o,o-EDDHA) isomers equally. However, strategy I plants took mainly the iron associated with the meso form (the lowest stability isomer).     

Sorption of 2,4-D and other phenoxy herbicides to soil, organic matter, and minerals

Purpose

We review 2,4-dichlorophenoxyacetic acid (2,4-D) and other phenoxy herbicide sorption experiments.

Methods

A database with 469 soil–water distribution coefficients K _d (in liters per kilogram) was compiled: 271 coefficients are for the phenoxy herbicide 2,4-D, 9 for 4-(2,4-dichlorophenoxy)butyric acid, 18 for 2-(2,4-dichlorophenoxy)propanoic acid, 109 for 2-methyl-4-chlorophenoxyacetic acid, 5 for 4-(4-chloro-2-methylphenoxy)butanoic acid, and 57 for 2-(4-chloro-2-methylphenoxy)propanoic acid. The following parameters characterizing the soils, solutions, or experimental procedures used in the studies were also compiled if available: solution CaCl₂ concentration, pH, pre-equilibration time, temperature, soil organic carbon content (f _oc), percent sand, silt and clay, oxalate extractable aluminum, oxalate extractable iron (Oxalate Fe), dithionite–citrate–bicarbonate extractable aluminum, dithionite–citrate–bicarbonate extractable iron (DCB Fe), point of zero negative charge, anion exchange capacity, cation exchange capacity, soil type, soil horizon or depth of sampling, and geographic location. K _d data were also compiled characterizing phenoxy herbicide sorption to the following well-defined sorbent materials: quartz, calcite, α-alumina, kaolinite, ferrihydrite, goethite, lepidocrocite, soil humic acid, Fluka humic acid, and Pahokee peat.

Results

The data review suggests that sorption of 2,4-D can be rationalized based on the soil parameters pH, f _oc, Oxalate Fe, and DCB Fe in combination with sorption coefficients measured independently for humic acids and ferrihydrite, and goethite.

Conclusions

Soil organic matter and iron oxides appear to be the most relevant sorbents for phenoxy herbicides. Unfortunately, few authors report Oxalate Fe and DCB Fe data.     

Iron and/or acid foliar spray versus soil application of Fe-EDDHA for prevention of iron deficiency in Valencia orange grown on a calcareous soil

A two-year experiment was conducted in an iron(Fe)-deficient orchard with calcareous soil to find out an alternate method for soil application of Fe ethylenediamine-N,N'-bis(2-hydroxyphenylacetic acid) (Fe-EDDHA) in orange trees. Foliar sprays of Fe-EDDHA (5 g l^?1, pH = 7.8), sulfuric acid (pH = 3), citric acid (5 g l^?1, pH = 2.4), Fe (II) sulfate solutions (250, 500, and 750 mg Fe l^?1) with their initial pH (6.5, 6.35, and 6.12) and reduced ones to pH of 3 were compared with soil applied (75 g tree^?1) Fe-EDDHA and a control test. Although optimum chlorophyll content, leaf Fe concentration, fruit quantitative and qualitative attributes were resulted from soil application of Fe-EDDHA, repeated sprays of Fe-EDDHA or acidified Fe solutions created suitable results. Acidification of Fe solutions made them more effective in alleviation of leaf Fe concentration and Fe chlorosis, probably due to remobilization of inactive Fe within the plant and prevention of Fe oxidation and precipitation in foliar solutions.     

Methodology to Screen New Iron Chelates: Prediction of Their Behavior in Nutrient Solution and Soil Conditions

Abstract

Iron chelates analogous to ethylenediamino‐di(o‐hydroxyphenyl)acetic acid (EDDHA) are the fertilizers chosen to treat iron chlorosis of crops grown on calcareous soils. Characterization of these synthetic ligands should be made to establish their chemical behavior and efficiency as chlorosis correctors. The aim of this research was to develop an appropriate methodology to screen new iron chelates using analytical determinations and chemical equilibrium concepts. Fe‐EDDHA, Fe‐EDDH4MA, Fe‐EDDH5MA, and Fe‐PDDHA chelates, were compared to check the proposed methodology. Titrimetric purity, protonation and Ca, Mg, and Fe(III) stability constants, pFe and species distribution in nutrient solution and soil conditions were determined. The iron chelate stability constants were in order EDDHA > EDDH4MA > EDDH5MA > PDDHA. When pFe was calculated, the larger value corresponds to Fe‐EDDHA chelate at pH below 8; but at pH above 8 the Fe‐EDDH4MA shows the larger pFe values. When the species was plotted against pH, the dominant species was FeL^? at the physiological pH range in all cases. The pH at a FeL/L_T ratio of 80% in both Fe(OH)_3amorp and Fe_soil systems was considered as an iron chelate stability index. This index was EDDH4MA > EDDH5MA > EDDHA > PDDHA in both systems, but shows that all of the chelates tested were sufficiently stable in most soil and nutrient solution conditions. In conclusion, the proposed procedure is adequate for the preliminary evaluation of the synthetic chelating agents, using important parameters such as analytical and speciation properties to predict their chelating behavior and efficiency in nutrient solution and soil conditions.     

Interaction of Iron with Copper,Zinc, and Manganese in Wheat as Affected by Iron and Manganese in a Calcareous Soil

Iron (Fe) availability is low in calcareous soils of southern Iran. The chelate Fe-ethylenediamine di (o-hydroxy-phenylacetic acid) (Fe-EDDHA), has been used as an effective source of Fe in correcting Fe deficiency in such soils. In some cases, however, its application might cause nutritional disorder due to the antagonistic effect of Fe with other cationic micronutrients, in particular with manganese (Mn). A greenhouse experiment was conducted to evaluate the influence of soil and foliar applications of Fe and soil application of manganese (Mn) on dry matter yield (DMY) and the uptake of cationic micronutrients in wheat (Triticum aestivum L. var. Ghods) in a calcareous soil. Results showed that neither soil application of Fe-EDDHA nor foliar application of Fe sulfate had a significant effect on wheat DMY. In general, Fe application increased Fe uptake but decreased that of Mn, zinc (Zn), and copper (Cu). Application of Mn increased only Mn uptake and had no significant effect on the uptake of the other cationic micronutrients. Iron treatments considerably increased the ratio of Fe to Mn, Zn, Cu, and (Mn + Zn + Cu). Failure to observe an increase in wheat DMY following Fe application is attributed to the antagonistic effect of Fe with Mn, Zn, and Cu and hence, imbalance in Fe to (Mn + Zn + Cu) ratio. Due to the nutritional disorder and imbalance, it appears that neither soil application of Fe-EDDHA nor foliar application of Fe-sulfate is appropriate in correcting Fe deficiency in wheat grown on calcareous soils. Hence, growing Fe-efficient wheat cultivars should be considered as an appropriate practice for Fe chlorosis-prone calcareous soils of southern Iran.     

Heavy metal sorption on soil minerals affected by the siderophore desferrioxamine B: the role of Fe(III) (hydr)oxides and dissolved Fe(III)

Phytoextraction of heavy metals from polluted soils has often been found to be limited by the bioavailability of the pollutants. Inorganic or organic ligands are occasionally used as complexing agents to enhance the mobility of the heavy metals. However, the opposite effect is also possible. We studied the influence of the hydroxamate siderophore desferrioxamine B (DFOB) on the sorption of Cu, Zn and Cd to clay minerals, with the emphasis on the role of dissolved Fe(III) and Fe(III) minerals. Depending on the surface charge of the minerals and on pH, sorption of heavy metals can be either enhanced or diminished. We show here that this effect of DFOB disappears if dissolved Fe(III) is added to suspensions of clay minerals in excess to DFOB. We found that the solid Fe(III) phases ferrihydrite and goethite did not impede the effect of DFOB on the sorption of heavy metal, however. Between pH 4 and 10, DFOB completely prevented Cu sorption on ferrihydrite. A strong mobilizing effect was also observed for Zn, but not for Cd. In presence of goethite, concentrations of dissolved Cu, Zn and Cd were enhanced only above approximately pH 5, 7 and 8, respectively. Below these pH values the binding of these metals to goethite was even stronger with than without DFOB. In the absence of heavy metals, DFOB‐promoted dissolution of ferrihydrite was much faster than that of goethite due to the larger surface area of ferrihydrite. In the alkaline pH range, where sorption of DFOB on the surfaces of the iron oxides was greater, dissolution of both minerals was reduced.     

Performance of soil-applied FeEDDHA isomers in delivering Fe to soybean plants in relation to the moment of application

FeEDDHA (iron(3+) ethylenediamine-N,N'-bis(hydroxyphenylacetic acid) products are commonly applied to mend and prevent Fe deficiency chlorosis in soil-grown crops. Plants mainly take up Fe in the progressed vegetative and in the reproductive stages. This study examined which of the principal constituents of FeEDDHA products (the isomers racemic o,o-FeEDDHA, meso o,o-FeEDDHA, and o,p-FeEDDHA), most effectively meets the Fe requirements of soybean plants (Glycine max (L.) Merr.) grown on calcareous soil in the aforementioned growth stages. FeEDDHA isomers were applied once, separately or in mixtures, at t = 0, in the progressed vegetative stage or in the reproductive stage. o,p-FeEDDHA did not significantly contribute to Fe uptake in either growth stage. Both racemic and meso o,o-FeEDDHA were effective in supplying plants with Fe, approximately to the same extent. The moment of application had a significant effect on yield and FeEDDHA pore water concentrations at harvest, but not on Fe uptake. To optimize yield while minimizing FeEDDHA dosage, FeEDDHA is best applied to soybean plants prior to the onset of chorosis.     

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.     

汞在泥炭上的吸附特征研究

采用批次法研究了汞在三江平原泥炭、吉林双阳泥炭上等温吸附特征及介质pH值、背景离子浓度的影响。实验结果表明:两种泥炭吸附等温线均同时符合Langmuir和Freundlich等温吸附方程,而与Langmuir方程的拟合效果更好; 在溶液汞浓度相同时,温度升高,泥炭对汞的吸附量降低;在相同的条件下,三江平原泥炭对汞的吸附量大于吉林双阳泥炭对汞的吸附量;两种泥炭对汞的吸附量受pH值的影响明显且都在pH 6.0左右具有最大的吸附量;在酸性条件下,吸附介质的pH值升高利于泥炭对汞的吸附;介质的离子浓度升高,可以使两种泥炭对汞的吸附量迅速降低。     

Sorption of organic acids in acid soils and its implications in the rhizosphere

Organic acids have been implicated in many soil-forming and rhizosphere processes, but their fate in soil is poorly understood. We examined the sorption of four simple short-chain organic acids (citric, oxalic, malic and acetic) in five acid soils and on synthetic iron hydroxide (ferrihydrite). The results for both soils and ferrihydrite indicated that the sorption depended on concentration in the following order of strength: phosphate >> oxalate > citrate > malate >> acetate. The sorption reactions in soil were shown to be little influenced by pH, whereas for ferrihydrite, sorption of all ligands increased strongly with decreasing pH. The sorption of organic anions onto ferrihydrite was influenced to a lesser extent by the presence of metal cations in solution. From the results we calculated that when organic acids enter solution they rapidly become sorbed onto the soil's exchange complex (> 80% within 10 min), and we believe that this sorption will greatly diminish their effectiveness to mobilize nutrients from the rhizosphere.     

Simple modelling of the sorption of iron‐cyanide complexes on ferrihydrite

The sorption of the iron‐cyanide complexes ferricyanide, [Fe(CN)₆]^3—, and ferrocyanide, [Fe(CN)₆]^4—, on ferrihydrite was investigated in batch experiments including the effects of pH (pH 3.5 to 8) and ionic strength (0.001 to 0.1 M). The pH‐dependent sorption data were evaluated with a model approach by Barrow (1999): c = a exp(bS)S/(S_max‐S), where c is the solution concentration; S is the sorbed amount; S_max is maximum sorption; b is a parameter; and a is a parameter at constant pH. Ferricyanide sorption was negatively affected by increasing ionic strength, ferrocyanide sorption not at all. More ferricyanide than ferrocyanide was sorbed in the acidic range. In the neutral range the opposite was true. Fitting the pH‐dependent sorption to the model resulted in a strong correlation for both iron‐cyanide complexes with a common sorption maximum of 1.6 μmol m^—2. Only little negative charge was conveyed to the ferrihydrite surface by sorption of iron‐cyanide complexes. The sorption of iron‐cyanide complexes on ferrihydrite is weaker than that on goethite, as a comparison of the model calculations shows. This may be caused by the lower relative amount of high‐affinity sites present on the ferrihydrite surface.     

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.