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1.
Mössbauer specttoscopy has been used to provide information on the effect of pH on the nature of the complexes formed between iron and humic acid. At an initial suspension pH greater than 3 the iron occurs in the ferric form, although it is difficult to assess to what extent it is in combination with organic matter. On lowering the pH, iron is reduced with a considerable proportion of the ferrous iron entering solution, partly as a solvated ion and partly as complex forms. Raising the pH leads to re-oxidation and the precipitation of a considerable proportion of the iron in an inorganic form with Mossbauer parameters similar to those of β-FeOOH. No evidence was obtained for Fe(III) in solution or for Fe(II) in any form at pH values greater than 4.  相似文献   

2.
Fulvic acids: structure and metal binding   总被引：1，自引：0，他引：1  
Equilibrium calculations have been carried out at 25°C and an ionic strength of 0.04 to determine the predominant metal binding sites on a well-characterized fulvic acid for magnesium(ll), calcium(ll), manganese(ll), iron(lll), copper(ll) and zinc(II). Statistical estimates of the concentration of 14 sites are obtained from a random molecular model of fulvic acid. Protonation and metal formation constants are estimated from those of simple model ligands and corrected to the above conditions. Results indicate the importance of phthalate sites for all metals except iron(III), salicylate sites for iron(lll) and acetylacetonate sites for copper(ll). Iron (III) ions are found to form ML2 type complexes extensively. The affinity of the metal ions for fulvic acid as a whole is found to decrease in the order iron(III) > copper(II) > zinc(II) > manganese(Il) > calcium(II) > magnesium (II).  相似文献   

3.
The ferric complexing capacity of four phenolic compounds, occurring in olives and virgin olive oil, namely, oleuropein, hydroxytyrosol, 3,4-dihydroxyphenylethanol-elenolic acid (3,4-DHPEA-EA), and 3,4-dihydroxyphenylethanol-elenolic acid dialdehyde (3,4-DHPEA-EDA), and their stability in the presence of ferric ions were studied. At pH 3.5, all compounds formed a reversible 1:1 complex with ferric ions, but hydroxytyrosol could also form complexes containing >1 ferric ion per phenol molecule. At pH 5.5, the complexes between ferric ions and 3,4-DHPEA-EA or 3,4-DHPEA-EDA were relatively stable, indicating that the antioxidant activity of 3,4-DHPEA-EA or 3,4-DHPEA-EDA at pH 5.5 is partly due to their metal-chelating activity. At pH 7.4, a complex containing >1 ferric ion per phenol molecule was formed with hydroxytyrosol. Oleuropein, 3,4-DHPEA-EA, and 3,4-DHPEA-EDA also formed insoluble complexes at this pH. There was no evidence for chelation of Fe(II) by hydroxytyrosol or its derivatives. At all pH values tested, hydroxytyrosol was the most stable compound in the absence of Fe(III) but the most sensitive to the presence of Fe(III).  相似文献   

4.
Previous studies have shown that organic acids have an impact on both Fe(II) and Fe(III) uptake in Caco-2 cell. However, to what extent this effect is correlated with the anion of organic acids per se, or with the resulting decrease in pH, has not yet been clarified. Therefore, we studied the effect of five organic acids (tartaric, succinic, citric, oxalic, and propionic acid) on the absorption of Fe(II) and Fe(III) in Caco-2 cells and compared this with sample solutions without organic acids but set to equivalent pH by HCl. The results showed that the mechanisms behind the enhancing effect of organic acids differed for the two forms of iron. For ferric iron the organic acids promoted uptake both by chelation and by lowering the pH, whereas for ferrous iron the promoting effect was caused only by the lowered pH.  相似文献   

5.
A comparative approach based on ion–selective electrode measurements is presented for studying Cu(II) complexing by fulvic acids. Metal binding curves (% free metal vs pH) and complexation capacity curves (% free metal vs total metal at fixed pH) for copper(II) fulvic acid systems are compared with those for appropriate model ligands.
It is inferred that citrate, malonate and amino acid moieties could dominate complexing to Cu(II) at pH 3 to 7. The involvement of amino acid moieties is supported by fluorescence quenching and by anodic stripping voltammetry (ASV) studies. The proportion of ASV–non labile complexes is reported for Cu(II) and Pb(II) fulvic acid systems at pH 4.8.
A mixed mode of coordination is proposed, with the dominant binding sites varying with pH and metal:ligand ratio.  相似文献   

6.
Fulvic acid is a water-soluble humic material that occurs widely in soils and waters and that tends to form water-soluble and water-insoluble complexes with a variety of metal ions, some of which are toxic. This paper presents information on the conditions under which the different types of FA-metal complexes are formed. The solubility in water, separately and after mixing, of FA (2 to 30 mg/100 ml) and eleven metal ions (Fe(III), Al, Cr(III), Pb, Cu, Hg(II), Zn, Ni, Co, Cd and Mn; 1 × 10?5 moles of each metal ion) was investigated over the pH range 4 to 9. After mixing, the solubility of the components was significantly affected by pH only when less than 20 mg of FA was present. As the systems became richer in FA (22 to 30 mg), most of the metal ions remained in the aqueous phase, likely due to the formation of FA-metal complexes, inhibiting the formation of metal hydroxides. The order in which the eleven metal ions tended to form water-insoluble FA-metal complexes depended on the pH. At pH 6 it was: Fe = Cr = Al > Pb = Cu > Hg > Zn = Ni = Co = Cd = Mn. This order appeared to correlate with the valence, 1st hydrolysis constants and effective hydrated ionic diameters of the metal ions. In general, FA/metals weight ratios of > 2 favored the formation of water-soluble FA-metal complexes; at lower ratios, water-insoluble complexes, which could accumulate in soils and sediments, were formed.  相似文献   

7.
《Journal of plant nutrition》2013,36(10-11):1909-1926
Abstract

Phenolic substances in the soil–plant system can be oxidized by metal ions, inorganic components, molecular oxygen as well as by phenoloxidases, giving rise to the formation of products of low or high molecular weight. Interactions of these products with iron, in both reduced and oxidized form, can affect the iron mobility in soil and rhizosphere, and thus its availability to plants. Here we report the results of a study on the complexing and reducing activity of the oxidation products from caffeic acid (CAF), obtained via electrochemical means, towards Fe(III) and Fe(II) in aqueous solution in the 3.0–6.0 pH range. The HPLC analysis of the filtered solutions after the CAF oxidation showed the formation of two main groups of products: (i) CAF oligomers formed through radicalic reactions which do not involve the double bond of the CAF lateral chain and (ii) products where this bond is involved. These oxidation products (COP) were found to interact with both Fe(III) and Fe(II) with formation of soluble and insoluble Fe(III)‐, and Fe(II)‐COP complexes. The COP were found to be able to reduce Fe(III) to Fe(II) mainly at pH < 4.0. A low redox activity was observed at pH ≥ 4.5 due to Fe(III) hydrolysis reactions as well as to the decrease in the redox potential of the Fe(III)/Fe(II) couple. Formation of hydroxy Fe(III)‐COP polymers occurs at pH > 3.5.  相似文献   

8.
Mössbauer and ESR spectroscopy have shown that the iron extracted from the Bh horizons of an iron humus podzol and an iron podzol by EDTA at pH 9.1 is predominantly in the form of complexes * 1 The use of the word ‘complex’ in this paper in the context of polymeric iron species and organic matter is not intended to imply any single specific type of complex, such as exists in Fe(II1) EDTA, for example, but to embrace many possible modes of association including salt formation, direct coordination, Van der Waal's adsorption, and electrostatic attraction.
of polymeric Fe(III) hydroxide and oxide with organic matter (O.M.). Small amounts of monomeric Fe(III)-O.M. and Fe(III)-EDTA complexes also occur. In contrast EDTA at pH 7 extracts iron from these podzols predominantly in the form of iron-EDTA complexes. Some monomeric Fe(III)-O.M. complex also occurs in a pH 9.1 NH4 OH extract of these horizons and in a pH 9.1 EDTA extract of the B3 horizon of a peaty podzol. Dialysis experiments show that the particle dimensions of the polymeric hydroxy Fe(III)-O.M. complex, which accounts for about 66% of the Fe extracted from the iron humus podzol and about 36% of that from the iron podzol, are greater than 2.4 nm. The thermal behaviour of the Mössbauer peaks indicated that the size of the iron cores was of the order of 5 nm, thus suggesting that the complex probably consists of hydroxyiron cores surrounded by large organic molecules. Results from XRD and IR suggest that these hydroxyiron cores may have structural organizations similar to those of goethite and ferrihydrite. The relationship between these forms of iron in the extracts and those in the soil is briefly discussed.  相似文献   

9.
《Journal of plant nutrition》2013,36(10-11):1927-1941
Abstract

The interaction between polygalacturonic acid and Fe(III) was studied in the presence and in the absence of pyruvic, malic, and citric acids. Kinetical data and FT‐IR analyses show that the polysaccharidic matrix acts as an accumulator of Fe(III) and that the metal ion interacts electrostatically with both the carboxylic and other functional groups of the polysaccharidic matrix. Copper(II) ions, which have a high affinity towards the carboxylic groups of the polysaccharide, do not influence markedly the Fe(III) absorption indicating that the carboxylic groups are not determining in the Fe(III) accumulation process. Furthermore, the results suggest that iron inside the fibrils is under an hydrolyzed form or as Fe(III) hydroxy polymer. In the presence of malic and citric acids the amount of Fe(III) accumulated at pH 4.7 and 6.0 is markedly lower than that found in the presence of pyruvic acid what was attributed to the higher affinity of citric and malic acid towards the metal ion.  相似文献   

10.
《Journal of plant nutrition》2013,36(10-11):1889-1908
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.  相似文献   

11.
The effect of sixteen metal ions: Al, Cd, Co(II), Cr(III), Cr(VI), Cu(II), Fe(III), Li, Mg, Mn(II), Mo(VI), Ni(II), Pb(II), Se(IV), V(V), and Zn on the mortality and infectivity ofHeterorhabditis bacteriophora were observed over a 96 hr period. All ions except Pb(II) even at naturally unrealistic concentrations did not cause the mortality of the nematodes. A weak vitalizing effect could eventually be observed with Mn(II), Mg, Fe(III) and Ni(II) (Table 1). However, such treatment generally lowered infectivity of the nematodes with respect to wax moth caterpillars.Galleria mellonella. This effect was particularly significant with Ni(II) and Pb(II).  相似文献   

12.
Water, soil and sediment contaminated with DDT poses a threat to the environment and human health. Previous studies have shown that zerovalent iron (ZVI) can effectively remediate water contaminated with pesticides like DDT, metolachlor, alachlor. Because the type of iron can significantly influence the efficiency and expense of ZVI technology, finding a cheaper and easily available iron source is one way of making this technology more affordable for field application. This study determined the effects of iron source, solution pH, and presence of Fe or Al salts on the destruction of DDT. Batch experiments demonstrated successful removal of DDT (>95% in 30 d) in aqueous solutions by three different iron sources with the following order of removal rates: untreated iron byproduct (1.524 d?1) > commercial ZVI (0.277 d?1) > surface-cleaned iron byproduct (0.157 d?1). DDT removal rate was greatest with the untreated iron byproduct because of its high carbon content resulted in high DDT adsorption. DDT destruction rate by surface-cleaned iron byproduct increased as the pH decreased from 9 to 3. Lowering solution pH removes Fe (III) passivating layers from the ZVI and makes it free for reductive transformations. By treating DDT aqueous solutions with surface-cleaned iron byproduct, the destruction kinetics of DDT were enhanced when Fe(II), Fe(III) or Al(III) salts were added, with the following order of destruction kinetics: Al(III) sulfate > Fe(III) sulfate > Fe(II) sulfate. Cost analysis showed that the cost for one kg of surface-cleaned iron byproduct was $12.33, which is less expensive than the commercial ZVI. Therefore, using surface-cleaned iron byproduct may be a viable alternative for remediating DDT-contaminated environments.  相似文献   

13.
Lactic acid (LA) has been proposed to be an enhancer for dietary iron absorption, but contradictory results have also been reported. In the present study, fully differentiated Caco-2 cell monolayers were used to evaluate the effects of LA (1-50 mmol/L) on the cellular retention and transepithelial transport of soluble non-heme iron (as ferric nitrilotriacetate). Our data revealed a linear decline in Fe(III) retention with respect to the concentration of LA added. In the presence of 50 mmol/L LA, retention of Fe(III) and Fe(II) decreased 57% and 58%, respectively. In contrast, transfer of Fe(III) across the cell monolayer was doubled, while Fe(II) transfer across the cell monolayer decreased 35%. We conclude that LA reduces cellular retention and transepithelial transport of Fe(II) by Caco-2 cells in a dose-dependent manner. However, while LA also reduces retention of Fe(III) by Caco-2 cells, the transfer of Fe(III) across cell monolayers is enhanced, possibly due to effects on paracellular transport.  相似文献   

14.
The objective of this study was to determine the ratio and amount of Fe II and Fe III iron in different parts of 20 and 40 day old bean plants grown in pots under normal and HCO-treatment. The Fe II and Fe III iron determination was carried out by a modification of a method described by Vogel (1969). The Fe II and Fe III concentrations in the plant varied according to its age, the plant part, the order of leaves and HCO-treatment. At the second sampling date, the lower total iron content in the lower leaf particularly under the HCO-treatment suggests that the supply of iron from the roots was restricted. The iron content of the different leaves was almost evenly divided into Fe II and Fe III at the first date. At the second date, most of the iron in the bud leaf was present as Fe II. Under HCO-treatment the Fe II content of the bud leaf and the flower was similar as in the corresponding parts of the normal green plants whereas the Fe III content was considerably lowered in these plant parts as result of the HCO-treatment. The results indicate a substantial retranslocation of iron from older to younger leaves and a higher Fe II/Fe III ratio in flowers and bud leaves particularly under HCO-induced chlorosis.  相似文献   

15.
Water-ex tractable poly carboxy lie acids and alkali-extractable humic acids and fulvic acids, were isolated from agricultural top-soils of two soil associations. Samples from four soil series from each association were selected with drainage status varying from well-drained to very poorly-drained. The amounts of atkali-extractable humic acid and water-ex tractable polycarboxylic acids were highest in the very poorly-drained soils whilst the amounts of alkali-extractable fulvic acid were generally similar in all the soils, although the fulvic acid accounted for a lower proportion of the total organic matter in the poorly-drained soils. Oxalate-extractable aluminium decreased with increased drainage impedance, whilst no such trend was observed for oxalate-extractable iron. It is suggested that the fulvic acid-like polycarboxylic acids are removed from the soil solution by adsorption onto sesquioxides; so that the lower content of aluminium oxides in the very poorly-drained soils results in depressed levels of fulvic acid and increased concentrations of water-extractable polycarboxylic acids.  相似文献   

16.
It has previously been suggested that organic acids enhance iron absorption. We have studied the effect of nine organic acids on the absorption of Fe(II) and Fe(III) in the human epithelial cell line Caco-2. The effect obtained was dose-dependent, and the greatest increase (43-fold) was observed for tartaric acid (4 mmol/L) on Fe(III) (10 micromol/L). Tartaric, malic, succinic, and fumaric acids enhanced Fe(II) and Fe(III) uptake. Citric and oxalic acid, on the other hand, inhibited Fe(II) uptake but enhanced Fe(III) uptake. Propionic and acetic acid increased the Fe(II) uptake, but had no effect on Fe(III) uptake. Our results show a correlation between absorption pattern and chemical structure; e.g. hydroxyl groups, in addition to carboxyls, were connected with a positive influence. The results may be important for elucidating factors affecting iron bioavailability in the small intestine and for the development of foods with improved iron bioavailability.  相似文献   

17.
Gleying and enhancement of hydromorphism in wetland soils due to Fe(III) reduction entail a series of degradation processes. The resistance of wetlands to degradation can be calculated from the content of potentially reducible iron, Fe(III)pr, which is found from the van Bodegom equation taking into account the contents of oxalate-soluble iron Feox and dithionite-soluble iron Fedit in the soil. In addition, this makes it possible to distinguish relict and actual gleysols. The van Bodegom equation is applicable to soils from which the oxalate solution extracts only amorphous and poorly crystallized iron compounds, which are quickly reduced by Fe-reducing bacteria. These soils have a low proportion of Fe(II) (no more that 15% of the total iron), as well as an accumulative profile distribution of Feox. The van Bodegom equation is unsuitable for calculating the Fe(III)pr content in soils with a high proportion of Fe(II) and a nonaccumulative profile distribution of Feox.  相似文献   

18.
The effect of the arbuscular mycorrhizal (AM) fungus (Glomus versiforme) on iron contents by two citrus rootstocks (trifoliate orange [Poncirus trifoliata L. Raf] and red tangerine [Citrus reticulata Blanco]) was studied in sand culture under different pH conditions. Seeds were sown in a mixed substrate (perlite/sand, 1:1 [v/v]) inoculated with or without mycorrhizal inoculum. The experiment was carried out at four pH levels by applying nutrient solution at pH 5.0, 6.0, 7.0, or 8.0 to P. trifoliata and pH 5.2, 6.2, 7.2, or 8.2 to C. reticulata. No AM colonization was found in uninoculated control (NM) and plants, and root colonization in AM plants was depressed under iron deficiency at high pH. Colonization by G. versiforme led to higher dry weights of shoots compared with NM treatments, suggesting that G. versiforme enhanced plant growth. Higher concentration of chlorophyll and active iron, lower ratios of P/Fe and 50(10P+K)/Fe were present in AM plants than NM treatments. Nevertheless, G. versiforme improved root Fe (III) chelate reductase activity of P. trifoliata and C. reticulata. The data indicate that plant uptake and translocation of iron were enhanced and AM fungi may be considered as a potential tool for bioremediation of citrus iron deficiency.  相似文献   

19.
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20.
The podzolization process is examined in the light of measurements of the solubility characteristics of aluminium fulvate, the extent of dissolution of a proto‐imogolite sol by fulvic acid, the adsorption capacity of proto‐imogolite for fulvic acid and aluminium fulvate, and published evidence. Fulvic acid at 500 mg l?1 acting on a proto‐imogolite (PI) preparation containing 0.95 mmol l?1 Al as PI did not bring enough Al into solution at pH 4.5–5.0 over 4–15 months to cause significant precipitation of the fulvic acid. As allophanic Bs horizons of podzols typically have pH ≥ 4.8, fulvic acids entering them in drainage water cannot be quantitatively precipitated by dissolution of Al from the allophane. They are, however, strongly absorbed on the allophane, and this must be the mechanism that removes most of the fulvic acid at the top of the Bs horizon, and which contributes, along with colloidal humus and root decomposition, to the formation of a Bh horizon. We conclude that fulvic acid plays no active role in podzolization, but only recycles Al and Fe, that have been transferred by biological processes to the O horizon, back to the Bh horizon. The podzolization process, which leads to the formation of an allophanic Bs horizon underlying a progressively deepening E horizon, requires the dissolution of Al‐humate and allophanic precipitates at the Bh–Bs interface as well as progressive attack on the more readily weatherable minerals. Inorganic acids, particularly episodic fluxes of nitric acid, could play a major role in this, as well as attack by readily metabolized complexing acids such as oxalic and citric acids released by roots and fungi. In addition to throwing light on the podzolization process, the experimental results provide an explanation of the lower limit to C:Al ratios reported in natural waters, and a check on the applicability of the WHAM chemical equilibrium model to Al–fulvate–proto‐imogolite equilibria. In Ca‐containing fulvate solutions, Al‐fulvate begins to precipitate when C:Al falls below 50, which is also the limiting ratio observed in natural waters. WHAM calculations overestimate by 70–85% the amount of Al‐fulvate formed over 4 months at pH 4.5–5.0 in Ca‐containing fulvate–imogolite systems.  相似文献   

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