The involvement of iron and aluminum in the bonding of phosphorus to soil humic acid

Abstract

With a peat soil similar amounts of phosphorus (P) were coprecipitated with humic acid from alkali extracts over a limited range of strongly acidic pH, whereas with a mineral soil the amount was pH dependent. The difference between the two soils relates to the much greater total amounts of inorganic P and aluminum (Al) present in the extract of the mineral soil. In this acid mineral soil, Al rather than iron (Fe) may be involved in the formation of metal bridges in humic acid‐metal‐inorganic P complexes. Neither Al or Fe were implicated in binding of organic P to humic acid. The P species observed in humic acids was dependent on the pH at which they were precipitated from the alkali extracts. In the peat soil the inorganic P was an order of magnitude lower than the organic P.     

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.     

Long-term reactions of Ni, Zn and Cd with iron oxyhydroxides depend on crystallinity and structure and on metal concentrations

Iron oxyhydroxides are long-term sinks for toxic trace metals and are suggested as factors to explain long-term metal immobilization in soil. It is unknown how crystallinity and crystal structure of iron (Fe) oxyhydroxides affect the long-term kinetics of trace metal adsorption. Adsorption kinetics of nickel (Ni), zinc (Zn) and cadmium (Cd) on to four synthetic Fe oxyhydroxides (hydrous ferric oxide (HFO), ferrihydrite (FH), goethite (GT), haematite (HT)) were characterized in suspensions during 70 days at different initial metal concentrations and various pH values (3.8–7.0) maintained within 0.2 units. The slow reactions, defined as those occurring beyond day 1 were most pronounced in GT and least in HT. The extent of the slow reaction was surprisingly unrelated to crystallinity or microporosity as determined by N₂ adsorption. Freundlich adsorption isotherms fitted to the data show that ageing between 1 and 70 days decreases metal concentrations in solution by factors of 2–30 (Ni), 1–20 (Zn) and 1–4 (Cd) depending on the type of oxyhydroxide. These factors become significantly larger at smaller concentrations for Ni and Zn in some oxyhydroxides and this concentration dependency suggests that slow reactions are not only related to diffusion. The short-term adsorption strength of carrier-free metal radio-isotopes was similar at 1 or 70 days after reaction with these iron oxyhydroxides and excludes the possibility that long-term reactions are related to solid-phase transformations or changes in solution properties. The extent of slow reactions in GT decreased with decreasing pH and was less than a factor 2 within 70 days at pH 3.7. The results confirm that slow reactions in Fe oxyhydroxides can explain lessened metal availability by ageing in pH neutral soils. The uncertainty of their actual structure and crystallinity in soils does not allow quantitative predictions based on the behaviour of synthetic oxyhydroxides.     

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.     

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.     

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.     

Determination of Mugineic Acid, 2′-Deoxymugineic Acid, 3-Hydroxymugineic Acid,and Their Iron Complexes by Ion-Pair HPLC and Colorimetric Procedures

Extract

Under iron (Fe)-deficient conditions like in calcareous and/or high pH soils, mugineic acid family phytosiderophores (MAs: mugineic acid (MA), 2′-deoxymugineic acid (DMA), 3-hydroxymugineic acid (HMA) etc.) are secreted from graminaceous plants and solubilize the slightly soluble Fe in soil as MAs-Fe complexes (Takagi 1976, 1993). Due to their high availability to higher plants (Roemheld and Marschner 1986), the behavior of MAs and their Fe complexes in the soil environment is of interest in connection with the iron nutrition of these plants.     

Precipitation of secondary phases of iron and its role in controlling the mobility of potentially toxic elements in soils in a semiarid river basin in Northwest Mexico

Purpose

Soils have the ability to retain potentially toxic elements (PTEs) through different chemical processes that promote low mobility of these elements, such as the precipitation of secondary phases of Fe, which facilitate the adsorption/co-precipitation of PTEs. The main objective of this study was to evaluate the mobility of PTEs present in an acid solution in two soils with different concentrations of calcite, understanding the role of secondary iron phases in the retention of these elements.

Materials and methods

To evaluate this phenomenon, intact soil columns of two different types of soils from the Sonora River in Northwest Mexico were exposed to an acid solution with high concentration of dissolved PTEs (mainly Fe, Al, and Cu).

Results and discussion

The Tinajas soil was free of carbonates while the Bacanuchi soil had more carbonate content than the Tinajas soil. Secondary precipitates corresponding to secondary phases of iron (mainly ferrihydrite and jarosite) were identified by X-ray diffraction. Using scanning electron microscopy, the PTEs retained in the soils were identified. The presence of calcite favored the neutral pH values in the collected leachates in the Bacanuchi soil; consequently, the mobility of the PTEs present in the acid solution was nullified. Furthermore, this process facilitated the retention of the toxic elements in the Bacanuchi soil.

Conclusions

The retention of PTEs was 100% in the Bacanuchi soil where the natural acid-neutralizing capacity in this soil was associated with calcite. The formation of secondary phases of Fe, among them ferrihydrite, jarosite, and schwertmannite, mainly in Bacanuchi soil, promoted the retention of Al, As, Cd, Cu, Fe, Mn, and Pb (elements analyzed in this work). Results of this work can provide key insights to improve cleanup and conservation strategies in mining sites.

     

Sorption of primisulfuron on soil, and inorganic and organic soil colloids

Inorganic and organic soil colloids are responsible for the sorption of many pesticides. We studied the sorption of the herbicide primisulfuron [methyl 2 N‐[[[[[4,6‐bis(difluoromethoxy)‐2‐pyrimidinyl]amino]carbonyl]amino]sulfonyl]benzoate] on Fe³⁺‐, Al³⁺‐, Ca²⁺‐ and Na⁺‐exchanged montmorillonite, soil organic matter (H⁺‐ and Ca²⁺‐saturated), amorphous iron oxide, and three soils in aqueous media. The sorption on soils was negatively correlated with pH. Ca²⁺‐ and Na⁺‐exchanged montmorillonites are ineffective in the sorption of primisulfuron. The sorption on Fe³⁺‐ and Al³⁺‐exchanged montmorillonite is rapid and follows the Freundlich equation. Fourier transform infrared (FT‐IR) and X‐ray powder diffraction studies of the Fe³⁺‐ and Al³⁺‐montmorillonite samples after the interaction with primisulfuron in chloroform solution suggest that primisulfuron is adsorbed and degraded in the interlayer. Humic acid is more effective in the sorption than is Ca humate, suggesting that the pH of the suspension (3.5 for humic acid and 6.0 for Ca humate) has a strong influence on the sorption of primisulfuron. Experiments on amorphous iron oxide indicate similar pH dependence. Infrared spectra indicate that the protonation of the pyrimidine nitrogen moiety of herbicide and subsequent hydrogen bonding with the surface hydroxyls of Fe oxide is the mechanism acting in the primisulfuron sorption.     

Adsorption and desorption of triasulfuron by soil

The adsorption and desorption of the herbicide triasulfuron [2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide] by three soils, soil organic matter (H(+) and Ca(2+)-saturated), and an amorphous iron oxide were studied. Adsorption isotherms conformed to the Freundlich equation. It was found that pH is the main factor influencing the adsorption in all of the systems. Indeed, the adsorption on soils was negatively correlated with pH. The highest level of adsorption was measured on soils with low pH and high organic carbon content. Moreover, it was found that humic acid is more effective in the adsorption compared with calcium humate (the pH values of the suspensions being 3.5 and 6, respectively). Experiments on amorphous iron oxide confirmed the pH dependence. Desorption was hysteretic on soils having high organic carbon content.     

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.     

Removal of Heavy Metals from Soil Components and Soil by Natural Chelating Agents. Part I: Displacement from Clay Minerals and Peat by L-Cysteine and L-Penicillamine

The β-thiol group containing amino acids L-cysteineand L-penicillamine were tested for their ability to releaseheavy metals (Cd, Cr, Cu, Hg, Ni, Pb, Zn) from bondings ontotypical soil components (peat, bentonite, illite) at neutral pHformed by batch adsorption procedure. Following equilibrationthe metal loaded sorbents were extracted by aqueous amino acidsolutions under various physico-chemical conditions.The extractability of metals from peat (metal contents between62.0 and 6170 mg kg^-1) increased in thepresence of L-penicillamine following the order Cr < Hg < Pb <Ni ≈ Zn ≈ Cd, ranging from 9% (Cr) to 97% (Cd).The extractability by L-cysteine was slightly lower, followingthe sequence Cr < Pb < Cd < Ni < Zn. In both cases the sequencesdid not correlate with the order of the stability constants ofthe corresponding amino acid complexes. The recovery of metalsfrom bentonite was higher generally. The extent of removal increased with increasing molar excess of the amino acids and,to a lower extent, with increasing extraction volume.Presumably initiated by oxidation of amino acids or by theformation of sparingly soluble polymeric metal complexes, theconcentrations of dissolved metals dropped after an agitationperiod of 2 to 24 hr in most of the extracts. Aspects of thisprocess were discussed in detail.     

Influence of pH, iron source, and Fe/ligand ratio on iron speciation in lignosulfonate complexes studied using Mössbauer spectroscopy. Implications on their fertilizer properties

Iron chlorosis is a very common nutritional disorder in plants that can be treated using iron fertilizers. Synthetic chelates have been used to correct this problem, but nowadays environmental concerns have enforced the search for new, more environmentally friendly ligands, such as lignosulfonates. In this paper, Fe coordination environment and speciation in lignosulfonate (LS) complexes prepared under different experimental conditions were studied by (57)Fe M?ssbauer spectroscopy in relation to the Fe-complexing capacities, chemical characteristics of the different products, and efficiency to provide iron in agronomic conditions. It has been observed that the complex formation between iron and lignosulfonates involves different coordination sites. When Fe(2+) is used to prepare the iron-LS product, complexes form weak adducts and are sensitive to oxidation, especially at neutral or alkaline pH. However, when Fe(3+) is used to form the complexes, both Fe(2+) and Fe(3+) are found. Reductive sugars, normally present in lignosulfonates, favor a relatively high content of Fe(2+) even in those complexes prepared using Fe(3+). The formation of amorphous ferrihydrite is also possible. With respect to the agronomical relevance of the Fe(2+)/Fe(3+) speciation provided by the M?ssbauer spectra, it seems that the strong Fe(3+)-LS complexes are preferred when they are applied to the leaf, whereas root uptake in hydroponics could be more related with the presence of weak bonding sites.     

Factors Affecting the Formation,Nature, and Properties of Iron Precipitation Products at the Soil–Root Interface

Abstract

A number of iron oxides (hematite, goethite, lepidocrocite, maghemite, and magnetite) or short‐range ordered precipitates (ferrihydrite) may be found in soil environments, but in the rhizosphere the presence of organic ligands released by plants (exudates) or microorganisms promote the formation of ferrihydrite. Iron ions are liberated into soil solution by acidic weathering of minerals and then precipitated either locally or after translocation in soil environments. Humic and fulvic acids as well as organic substances produced by plants and microorganisms are involved in the weathering of primary minerals. Organic compounds play a very important role in the hydrolytic reactions of iron and on the formation, nature, surface properties, reactivity, and transformation of Fe oxides. Organic substances present in the rhizosphere interact with Fe promoting the formation of ferrihydrite and organo‐mineral complexes. The solubility of Fe precipitation products is usually low. However, the formation of soluble complexes of Fe(II) or Fe(III) with organic ligands, usually present in the rhizosphere increases the solubility of Fe‐oxides. Mobilization of Fe from Fe oxides by siderophores is of great importance in natural systems. They can form stable Fe(III) complexes (pK up to 32) and thus mobilize Fe from Fe(III) compounds. These higher Fe concentrations are important for the supply of Fe to plant roots which excrete organic acids at the soil–root interface. Iron oxides adsorb a wide variety of organic and inorganic anions and cations, which include natural organics, nutrients, and xenobiotics. There is competition between anions and cations for the surfaces of Fe‐oxides. Root exudates suppress phosphate or sulfate adsorption on Fe‐oxides. This is a mechanism by which plant roots mobilize adsorbed phosphate and improve their phosphate supply. Anions adsorption on iron oxides modify their dispersion/flocculation behavior and thus their mobility in the soil system. That can increase or decrease the possibility of contact between Fe‐oxides and organics or organisms able to dissolve them.     

Iron oxide mineralogy of Terre Rosse and Rendzinas in relation to their moisture and temperature regimes

Terre Rosse and Rendzinas occur on limestones close together under the same climatic conditions. Their differences in iron oxide mineralogy are believed to be due to differences in the pedoclimate. We monitored the soil moisture tension and the soil temperature over nearly 3 years in Terra Rossa-Rendzina pairs on hard limestone and soft chalk in Israel. The Terre Rosse dried out more rapidly than the Rendzinas mainly because of their smaller water-holding capacity. In summer, average soil temperatures in the Rendzinas were significantly lower than in the Terre Rosse. Haematite dominates the red Terre Rosse and goethite the yellower Rendzinas. This difference appears to be related to the soil climate, specifically the moisture regime of the two soils, and supports the hypothesis that release of Fe and formation of ferrihydrite in Terre Rosse during the wet winter is followed by transformation to haematite during marked desiccation in the dry summer. By contrast, wetter soil conditions in the Rendzinas direct the formation of Fe oxides more towards goethite. either directly or by transformation of ferrihydrite via solution.     

Solubility Relationships of Iron and Evaluation of its Fertility Status in Degraded Soils

This study was conducted to determine the solubility of iron (Fe) and identify the solid phases responsible for controlling its solubility in these soils by using Baker soil test (BST) computer program. The results indicated that the ferric ion (Fe³⁺) activity in all the soils, except the acidic ones, nearly approached the theoretical solubility line of known minerals, namely soil-Fe, amorphous-Fe, maghemite, and lepidocrocite. Solubility of Fe in acid soils of Ranchi (soil 3) and Cooch-Behar (soil 6) did not match the theoretical solubility lines of any of the known minerals. The acidic soils of Ranchi and Cooch-Behar were sufficient for Fe with respect to both quantity and intensity factor based on BST rating, while alkaline (soil 1) and calcareous (soil 5) were sufficient in reserve Fe; deficiency of iron still could be suspected because of high pH. These findings elucidate the role of solid phase controlling iron solubility in soil solution of degraded soils.     

Ferrihydrite in soils

Ferrihydrite—an ephemeral mineral—is the most active Fe-hydroxide in soils. According to modern data, the ferrihydrite structure contains tetrahedral lattice in addition to the main octahedral lattice, with 10–20% of Fe being concentrated in the former. The presence of Fe tetrahedrons influences the surface properties of this mineral. The chemical composition of ferrihydrite samples depends largely on the size of lattice domains ranging from 2 to 6 nm. Chemically pure ferrihydrite rarely occurs in the soil; it usually contains oxyanion (SiO1₄^4-, PO₄^3-) and cation (Al³⁺) admixtures. Aluminum replace Fe³⁺ in the structure with a decrease in the mineral particle size. Oxyanions slow down polymerization of Fe³⁺ aquahydroxomonomers due to the films at the surface of mineral nanoparticles. Si- and Al-ferrihydrites are more resistant to the reductive dissolution than the chemically pure ferrihydrite. In addition, natural ferrihydrite contains organic substance that decreases the grain size of the mineral. External organic ligands favor ferrihydrite dissolution. In the European part of Russia, ferrihydrite is more widespread in the forest soils than in the steppe soils. Poorly crystallized nanoparticles of ferrihydrite adsorb different cations (Zn, Cu) and anions (phosphate, uranyl, arsenate) to immobilize them in soils; therefore, ferrihydrite nanoparticles play a significant role in the biogeochemical cycle of iron and other elements.     

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.     

Characterization of iron oxides in Fe-rich concretions from an imperfectly-drained Greek soil: a study by selective-dissolution techniques and X-ray diffraction

Fe-rich concretions commonly occur in Greek soils with alternating drying and waterlogging periods. This study was conducted to characterize the iron oxides in Fe-rich concretions from the upper solum of an Alfisol with seasonal perched water table by the combination of selective dissolution and X-ray diffraction (XRD) techniques. The results showed that more than 75% of the total iron (Fet) was associated with the crystalline and the amorphous Fe oxides, indicating a strong accumulation of free iron oxides (Fed) in concretions. Amorphous iron compounds (Feo) was present at high concentrations and fluctuated with profile depth. The active Fe ratio (Feo/Fed) values that ranged from 0.35 to 0.41 reflected an association of poorly crystalline goethite with some ferrihydrite. The XRD data showed that the Fe-rich concretions consisted of quartz, feldspars, illite and gypsum. The mineralogy of iron oxides in concretions was determined by comparison of XRD patterns for dithionite-citrate-bicarbonate (DCB) treated (deferrated) and untreated (non-deferrated) samples. Poorly crystalline goethite as demonstrated by broad lines in the diffraction patterns and ferrihydrite were the iron oxides detected in the concretions. This mineral assemblage appears to be related to the pedoenvironmental conditions in which the concretions were formed and indicates that the mechanisms governing the formation of crystalline Fe oxides from ferrihydrite are retarded by the presence of crystallization inhibitors.     

Fe(III)-EDDHA and -EDDHMA sorption on Ca-montmorillonite, ferrihydrite, and peat.

The effectiveness of Fe chelates as Fe sources and carriers in soil can be severely limited by the adsorption of Fe chelates or chelating agents in the solid phase. To study this phenomenon, well-characterized peat, Ca-montmorillonite, and ferrihydrite were used as model compounds, and the adsorption of Fe-EDDHA and Fe-EDDHMA chelates were studied. Sorption isotherms for the meso and racemic isomers of these chelates on the soil materials are described. The variability of sorption with pH in peat and ferrihydrite was also determined because both have variable surface charge at different pH values. In montmorillonite, at low concentrations, the retention of Fe from the Fe-EDDHMA chelate is greater than the one of the Fe-EDDHA chelate. As well as the concentration increased, the inverse situation occurs. The behavior of both meso and racemic isomers of chelates in contact with Ca-montmorillonite is similar. The Fe-meso-EDDHA isomer was highly adsorbed on ferrihydrite, but the racemic isomer is not significantly retained by this oxide. For Fe-EDDHMA isomers, the racemic isomer was more retained by the oxide, but a small sorption of the racemic isomer was also observed. Results suggest that Fe-EDDHA chelates were more retained in peat than Fe-EDDHMA chelates. The most retained isomer of Fe-EDDHA was the meso isomer. For Fe-EDDHMA, the adsorption was very low for both racemic and meso isomers.