Standard potentials (Eo) of iron(III) oxides under reducing conditions

Partial reduction of iron(III) oxides with hydrogen in the presence of a platinum catalyst leads to an equilibrium state after 4–20 h. From the measured Eh, pH, and Fe²⁺ concentration conditional standard potentials can be calculated using the formula E_o (volt) = Eh + 0.059 lg(Fe²⁺) + 0.18 pH which indicate the stability of Fe oxides against reduction. The reduceability decreases following the order ferrihydrite > lepidocrocite > hematite > goethite. The difference between hematite and goethite was more pronounced than that predicted from thermodynamic data.     

Redoxpotentiale und redoxprozesse von mangan-, eisenund schwefelverbindungen in hydromorphen böden und sedimenten

Results of laboratory experiments with soil material saturated with sea water indicate that, as predicted by thermodynamics, manganese (III, IV)-oxides are first reduced to Mn²⁺-ions (beginning at about +450 mV at pH 6.1.; E₇ ≈ +400 mV), next amorphous iron (III)-oxides are reduced to Fe²⁺-ions (beginning at about +220 mV at pH 6.0; E₇ ≈ +160 mV), and finally sulphates are reduced to sulphides (beginning at about +10 mV at pH 6.0; E₇ ≈ -50 mV). Direct quantitative relations between redox potentials, pH-values and Mn²⁺- (or Fe²⁺-) contents of water-saturated soils and sediments and calculated redox reactions of known manganese and iron systems could not be established.The influence of organic redox systems produced by microbial fermentation processes on the measured potentials and on the reduction of manganese and iron oxides is discussed.A reduction of the oxides by microbially formed sulphides, which themselves are oxidized by this process, seems also to be possible. Therefore, sulphides do not occur as stable sulphur phase in higher amounts before all available Fe-oxides are reduced to Fe²⁺-ions. Then formation of iron monosulphides takes place by precipitation of Fe²⁺- ions by sulphides (H₂S, HS). In a sulphide-stabilized environment redox reactions of sulphur — especially the reaction H₂S_aq = S₀ + 2 H⁺ + 2 e^? — may determined the measured potentials.The results show that the dynamics and morphology of hydromorphic soils and sediments are strongly dependent on microbial processes.     

Reductive dissolution of crystalline and amorphous Fe(III) oxides by microorganisms in submerged soil

Summary Reduction of Fe(III) of amorphous and crystalline Fe(III) oxides to Fe(II) in flooded soils was studied using ⁵⁹Fe(OH)₃ and ⁵⁹Fe₂O₃. The results indicated that Fe(III) in the amorphous oxide was readily amenable to microbial reduction in anaerobic soil condition whereas Fe(III) in the crystalline oxide was not. Following soil submergence, the native as well as the applied crystalline Fe(III) oxides were rapidly converted into the amorphous form. The transformation of the crystalline oxides to the amorphous form appears to be a prerequisite for the reduction of Fe(III) of the oxide. This transformation, probably through hydration, is also mediated by microorganisms.     

Differenzierung oxalatlöslicher Eisenoxide

Differentiation of oxalate soluble iron oxides According to their mode of formation the oxalate soluble Fe(III)-oxides show different rates of dissolution especially within the first 30 min of oxalate extraction. Precipitates formed by bacterial or oxidative decomposition of ferric citrate have a very high dissolution rate with more than 90 percent being dissolved within 30 min. Ferrihydrites prepared by alkaline hydrolysis of Fe(III) salts, after slow drying, dissolve to about 60 to 80 percent within this period, whereas similar products quenched with liquid N₂ dissolve more rapidly. A plot of (Fe₃₀/Fe_o) vs. (Fe_o/Fe_d) allows to draw a boundary line between the field of podzol values and the field of the other pedogenic iron oxides, as from brown earths and black earths (chernozems).     

Specific features of iron behavior in soddy-podzolic and alluvial gleyed soils of the Middle Cis-Urals region

The regime of observations revealed that the Eh dynamics in soddy-podzolic and alluvial soils in the Middle Cis-Urals region depends not only on the rate of iron (hydr)oxides reduction but also on the rate of opposite reactions in the gleyed horizons. Both processes depend on the temperature. The Eh value decreases on heating in automorphic soils, when the reduction of Fe(III)-(hydr)oxide particles accelerates. On the contrary, in gley soils, the Eh decreases on cooling, probably, because of the reactions opposing the reduction of Fe(III)-(hydr)oxide particles, including Fe(II) fixation on the surface of mineral particles. Fe(III)-(hydr)oxides are, for the most part, preserved in gleyed soils of the Cis-Urals; the content of (Fe₂O₃)_dit reaches 3.3% with iron minerals being usually represented by goethite. The increase in moistening influences the soil parameters (i.e., the redoxpotential rH and the content of conventional red pigment Hem_conv) in an intricate manner. Both direct and reverse branches on the curve of the Hem_conv-rH dependence point to the equilibrium and nonequilibrium conditions in the soil. The reverse branch probably stands for the initial phase of gleying in strongly humified soils, where, despite extra electrons in the solution, the brown pigment in the form of Fe(III)-(hydr)oxides is preserved.     

Methane and water soluble iron production under controlled soil pH and redox conditions

Abstract

When a soil is flooded, iron (Fe) reduction and methane (CH₄) production occurred in sequence as predicted by thermodynamics. The dissolution and precipitation of Fe reflected both soil pH and soil redox potential (Eh). The objective of our experiment was to determine both CH₄ production and Fe reduction as measured by Fe in solution in a flooded paddy soil over a wide range of closely controlled pH and Eh conditions. The greatest release of CH₄ gas occurred at neutral soil pH in combination with low soil redox potential (‐250 mV). Production of CH₄ decreased when soil pH was lowered in combination with an increase in the soil redox potential above ‐250 mV. Highest concentration of ferrous‐iron (Fe²⁺) under reducing conditions occurred when soil pH was lowered. Thus Fe reduction influenced CH4 formation in the flooded paddy soil. Results indicated that CH₄ production was inhibited by the process of ferric‐iron (Fe³⁺) reduction.     

Iron-cyanide complexes in soil under varying redox conditions: speciation, solubility and modelling

The distribution of iron‐cyanide complexes between ferrocyanide, [Fe^II(CN)₆]^4–, and ferricyanide, [Fe^III(CN)₆]^3–, in soils on contaminated sites depends on the redox potential, E_H. We carried out microcosm experiments in which ferrocyanide (20 mg l^?1) was added to an uncontaminated moderately acidic subsoil (pH 5.2), and varied the E_H of the soil suspension between 200 and 700 mV over up to 109 days. Ferrocyanide and ferricyanide were analysed by capillary isotachophoresis. At redox potentials ranging from 400 to 700 mV, small amounts of iron‐cyanide complexes were adsorbed, and ferrocyanide was almost completely oxidized to ferricyanide. Decreasing E_H to 200 mV led to nearly complete removal of iron‐cyanide complexes from solution, and the complexes were not mobilized after subsequent aeration (E_H > 350 mV). Under weakly to moderately reducing conditions (E_H ≈ 200 mV), iron‐cyanide complexes were removed from solution by precipitation, which occurred, presumably in the form of e.g. Fe₂[Fe^II(CN)₆], Fe₄[Fe^II(CN)₆]₃ or Mn₂[Fe^II(CN)₆], after reductive dissolution of Mn and Fe oxides. Four different sets of geochemical model calculations were carried out. The species distribution between ferrocyanide and ferricyanide in solution was predicted reliably under varying pH and redox conditions when iron‐cyanide complex concentrations and Fe concentrations, excluding Fe bound in iron‐cyanide complexes, were used in model calculations. In model calculations on the fate of iron‐cyanide complexes in soil, adsorption reactions must be considered, especially under oxidizing conditions. Otherwise, the calculated iron‐cyanide complex concentrations are larger than those actually measured.     

Potential Iron and Phosphate Mobilization During Flooding of Soil Material

This study shows that mobilization of phosphate from soils under anaerobic conditions can be intimately coupled with reductive dissolution of iron from iron oxides. Among four soil samples from the reclaimed Skjernå estuary in Denmark incubated anaerobically and amended with glucose, 28–39% of the dithionite-citrate-bicarbonate-extractable iron and 10–25% of the oxalate-extractable phosphorus (P_ox) were released to the soil solution after 31 days. Significant correlation (r = 0.992**) between the molar ratio P_ox/(Fe_ox + Al_ox) for the aerobic samples and (P_{P sol}/Fe_sol) (the molar ratio between phosphate and iron in solution during anaerobic incubation), indicates that the phosphate saturation status of the soil is an important determinant of the amount of phosphate released during flooding of moderately acid soils.     

Fe,Al, Mn,and S chemistry of Sphagnum peat in four peatlands with different metal and sulfur input

Comparisons among 4 peatland sites representing a gradient of increasing Fe, Al, Mn, and S loading revealed significant accumulation of total Fe, Al, and S, but not Mn, in surface (0 to 20 cm deep) peat along the gradient. Iron and Al accumulation were contributed mainly by organically bound fractions, with oxides contributing to a lesser extent. Although SO₄ ^2? and Fe sulfides showed significant increases in concentration along the gradient, most of the accumulation of total S was contributed by organic, rather than inorganic S. Laboratory studies of Fe²⁺ adsorption by peat indicated that increasing the pH of added Fe²⁺ solutions (pH values of 3, 4, 5, and 6) did not significantly affect Langmuir equation estimates of either maximum Fe²⁺ adsorption capacity or the affinity of peat for Fe²⁺. Regardless of the pH of the added Fe²⁺ solutions, final solution pH values were relatively uniform, averaging about 3.4, reflecting a considerable bufferring capacity of Sphagnum peat. Factors affecting the accumulation of metals and S in peat remain topics for further investigation.     

Disputable issues in interpreting the results of chemical extraction of iron compounds from soils

In Russia, iron is chemically fractionated according to a parallel scheme. Pyrophosphate-soluble iron (Fe_pyr) is considered to participate in organomineral complexes, oxalate-soluble iron (Fe_ox) is believed to enter amorphous + poorly crystallized compounds, and dithionite-soluble iron (Fe_dit) is meant to represent the free (nonsilicate) compounds. However, the investigations prove that the commonly used subtraction operations (Fe_ox ? Fe_pyr) and (Fe_dit ? Fe_ox) are invalid because of the nonadditive action of the reagents in the parallel scheme of extraction. The low selectivity of reagents requires a new interpretation of chemically extracted iron compounds. In automorphic soils, the content of oxalate-soluble iron should be interpreted as the amount of Fe(III) capable of complexing with organic ligands; in hydromorphic soils with a stagnant moisture regime, it should be interpreted as the amount of iron (III) capable of being reduced in a short time. The content of dithionite-soluble compounds should be regarded as the amount of iron (III) within both (hydr)oxides and silicates potentially prone to reduction.     

Diagnostics of gleyzation upon a low content of iron oxides (Using the example of tundra soils in the Kolyma Lowland)

The matrix of iron (hydr)oxides exerts a decisive influence on the character of gleyzation. Upon a high content of iron (hydr)oxides, their reduction radically changes the horizon color from warm to cold hues, which is typical of soils on the Russian Plain. Upon the low content of iron (hydr)oxides, iron reduction takes place in phyllosilicates with minimal changes in the soil color. The cold hue of cryohydromorphic soils in the Kolyma Lowland is controlled by the color of the lithogenic matrix with a low content of iron (hydr)oxides. In this case, the soil color characteristics expressed in the Munsell notation or in the CIE-L*a*b* system are ineffective for diagnostic purposes. The colorimetric methods appear to be more efficient after the soil pretreatment with hydrogen peroxide, as the gleyed horizons turn green, while the nongleyed (and not overmoistened) horizons turn red. Physical methods (Mössbauer spectroscopy and magnetic susceptibility measurements) are more efficient for characterizing the properties of iron compounds in cryohydromorphic soils as compared with the methods of chemical extraction. Mössbauer spectroscopy proved to be highly efficient, as the iron oxidation index Fe³⁺/(Fe²⁺+Fe³⁺) decreases in the gleyed horizons. Chemical reagents (Tamm’s and Mehra-Jackson’s reagents) dissolve Fe-phyllosilicates and are not selective in soils with a low content of iron (hydr)oxides.     

Effects of sodium hydroxide—selective chemical treatment on samples from some chilean soils

Abstract

The 5 Msodium hydroxide (NaOH) chemical treatment was applied to the silt and clay fractions of three Chilean fertilized soils derived from volcanic materials (one Ultisol and two Andisols) in order to selectively concentrate iron oxides. The treatment was sequentially applied and results were followed by x‐ray diffraction and Mössbauer spectroscopy. In all samples, dissolution chemical treatment concentrated iron oxides in variable degrees; and both, Mössbauer spectra and x‐ray diffraction patterns were significantly improved after three successive hot NaOH treatments. Best results were obtained for the Ultisol sample which is the oldest soil with the lowest organic matter content. The Mössbauer spectrum after three NaOH treatments of Ultisol silt fraction reveals characteristic features of partially oxidized magnetite, leading to two probability profiles of the hyper‐fine field distribution: One of them due to mixed valence iron (Fe^3+/2+) ions in octahedral sites [8=0.59 mm s^‐1, 2≥ Q =0.02mm s ‐1, with a maximum hyper‐fine field at B_hf(max)=46.2 tesla]; the other distribution profile encompasses contribution from Fe³⁺ in tetrahedral sites [δ=0.30 mm s^‐1, 2?Q =‐0.04 mm s^‐1 , and B_hf(max)=48.2 tesla].     

The influence of vegetation and soil type on the speciation of iron in soil water

Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe – DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe²⁺) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide‐rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well‐drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.     

Dissolution of Poorly Crystalline Iron Oxides in Soils by EDTA and Oxalate

Poorly crystalline iron oxides in soils are often estimated by 2 hours oxalate extraction at pH 3 and less often by 3–7 months EDTA extraction at pH 7.5–10.5. Calculated solubility products (Ksp) of iron oxides in equilibrium with EDTA and oxalate showed EDTA to dissolve only iron oxides with Ksp > 10^?40-10^?41 at pH > 10, whereas at pH 3 oxalate (and EDTA) should theoretically dissolve all iron oxides. The different pHs could largely account for the great difference in extraction speed between the two methods. Although EDTA and oxalate seem to act by surface complexation, where the adsorbed ligand by attenuating lattice Fe-O bonds causes iron detachment, the mechanisms are considered to be different. Possibly EDTA forms tetranuclear surface complexes, which are considered to inhibit dissolution of well crystallized but not poorly crystallized iron oxides due to differences in bond strengths. Oxalate forming binuclear and mononuclear surface complexes can probably also act as an electron bridge between iron(II) in solution and surface iron(III) leading to iron(II) catalyzed dissolution of iron oxides. This mechanism is obviously of particular importance in the dissolution of magnetite and maghemite. Despite the great theoretical differences the published methods with EDTA and oxalate dissolve comparable amounts of iron from many soils and the dissolved iron corresponds to poorly crystalline (highly reactive) iron oxides, mainly ferrihydrite.     

几种氧化铁的离子吸附特性研究

氧化铁是土壤中常见的氧化物,其中较为普遍的是针铁矿和赤铁矿,在某些土壤中也含有纤铁矿和无定形氧化铁.它们通常以极小的颗粒单独存在,或以胶膜状包裹在其它矿物颗粒的外面,有较大的比表面积,易受环境的影响,因此具有较高的活性,并对许多土壤的物理化学性质产生重要的影响.某些重金属离子和某些污染物进入土壤后的动向和行为也深受土壤中氧化铁的影响.     

Temperature-dependent oxide removal from manganese- and iron oxide-coated soil redox bars

Purpose

Soil temperature is a fundamental parameter affecting not only microbial activity but also manganese (Mn^III,IV) and iron (Fe^III) oxide reduction rates. The relationship between Mn^III,IV oxide removal from oxide-coated redox bars is missing at present. This study investigated the effect of variable soil temperatures on oxide removal by Mn^III,IV and Fe^III oxide-coated redox bars in water-saturated soil columns in the laboratory.

Materials and methods

The Mn coatings contained the mineral birnessite, whereas the Fe coatings contained a mixture of ferrihydrite and goethite. Additionally, platinum (Pt) electrodes designed to measure the redox potential (E_H) were installed in the soil columns, which were filled with either a humic topsoil with an organic carbon (C_org) content of 85 g kg^?1 (pH 5.8) or a subsoil containing 2 g C_org kg^?1 (pH 7.5). Experiments were performed at 5, 15, and 25 °C.

Results and discussion

Although elevated soil temperatures accelerated the decrease in E_H after water saturation in the topsoil, no E_H decreases regardless of soil temperature occurred in the subsoil. Besides soil temperature, the importance of soil organic matter as an electron donor is highlighted in this case. Complete removal of the Mn^III,IV oxide coating was observed after 28, 14, and 7 days in the soil columns filled with topsoil at 5, 15, and 25 °C, respectively. Along the Fe redox bars, Fe^III reducing conditions first appeared at 15 °C and oxide removal was enhanced at 25 °C because of lower E_H, with the preferential dissolution of ferrihydrite over goethite as revealed by visual differences in the Fe^III oxide coating. Oxide removal along redox bars followed the thermodynamics of the applied minerals in the order birnessite > ferrihydrite > goethite.

Conclusions

In line with Van’t Hoff’s rule, turnover rates of Mn^III,IV and Fe^III oxide reduction increased as a result of increased soil temperatures. Taking into account the stability lines of the designated minerals, E_H-pH conditions were in accordance with oxide removal. Soil temperature must therefore be considered a master variable when evaluating the oxide removal of redox bars employed for the monitoring of soil redox status.

     

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.     

Forms and pedogenic distribution of extractable iron in selected wetland soils in Nigeria

Abstract

The content of various forms of iron (Fe) (free, reducible, and organic) were determined by selective extraction methods in three wetland profiles between 1993 and 1995 seasons. The result showed that Fe distribution was in the order: dithionite (Fe_d) > hydroxylamine (Fe_H) > pyrophosphate (Fe_p) iron in the three pedons. The hydroxylamine‐Fe constituted between 10–42% (1993), 20–47% (1994), and 10–12% (1995) of the total free Fe oxides. The pyrophosphate‐Fe, on the other hand, constituted between 0.2–1.0% (1993), 19–52% (1994), and 3–9% (1995) of the total free Fe oxides. Dithionite‐Fe (total free iron oxides) content increases with the increasing depth, while hydroxylamine‐Fe decreases, suggesting that larger proportions of Fe oxides are present as crystalline forms in the lower horizons. The active Fe ratios were generally high in the top soils and low in the subsoil. It ranged between 0.03 and 0.69 (1993), 0.05 and 68 (1994), 0.05 and 0.53 (1995) in all pedons. This suggests that poor drainage slowed down soil development. Highly significant correlations (0.1%) were evident between phosphorus (P) and organic carbon; ECEC and base saturation; Fe_H and active Fe ratio. Significant correlations (1%) were also evident between Fe²⁺ and organic carbon; P and Fe_H; ECEC and clay. Furthermore, significant correlations (5%) were also obtained between clay and Fe_d; pH and Fe_d; active Fe ratio and P; Fe_H and clay; active Fe ratio and Fe_d.     

Iron and sulfate reduction in the sediments of acidic mine lake 116 (Brandenburg,Germany): Rates and geochemical evaluation

A combination of rate measurements of iron(III)oxide and sulfate reduction, thermodynamic data, and pore-water and solid phase analyses was used to evaluate the relative significance of iron and sulfate reduction in the sediments of an acidic strip mining lake (Lake 116, Brandenburg, Germany). The rate of sulfate reduction was determined using a 35S-radiotracer method. Rates of iron turnover were quantified by mass balances based on pore-water concentration profiles. The differences in Gibbs free energy yield from reduction of iron and sulfate and from methanogenesis were calculated from individual redox couples and concentrations of reactants to account for the influence of high Fe2+ concentrations and differing mineral phases. Integrated (O-20 cm) mean rates of sulfate reduction were 1.2 (pelagial), respectively 5.2 (littoral) mmol (m2d)-1. Based on electron equivalents, the estimated iron reduction rates reached between about 50 % (pelagial) and 75 % (littoral) of the sulfate reduction rates. Compared to conditions usually assumed in the literature, in the sediments Gibbs free energy advantage of iron reduction over sulfate reduction was reduced frmm +11 KJeq-1 to a range of about +7 KJeq-1 (ferrihydrite, "reactive iron") to -6 KJeq-1 (goethite). This indicates that iron reduction was thermodynamically favored to sulfate reduction only if amorphous iron(III)oxides were available and is in accordance to the high competitiveness of sulfate reducers in the sediment. While total iron concentration in the sediments was high (up to 80% of the dryweight), reactive iron only accounted for 11-38% and was absolutely and relatively diminished in the zone of iron reduction. Pore-water concentration gradients and 137CS profiles indicated that little or no bioturbation occurred in the sediments, probably inhibiting the renewal of reactive iron. We further hypothesize that the reactivity of the iron oxide surfaces was reduced due to adsorption of DOM, suggested by IR spectra of the DOM and by a surface coverage estimate using literature data. Pelagial and littoral sediments displayed different dynamics. At the littoral relative iron reduction rate estimates were higher, iron sulfides were not accumulated and residence times of iron oxides were short compared to the pelagial. At the littoral site reoxidation of iron sulfides probably resulted in the renewal of reactive iron(III)oxides, possibly allowing for higher relative rates of iron reduction.     

Changes of redox and pH conditions in a flooded soil amended with glucose and manganese oxide or iron oxide under laboratory conditions

The changes of Eh and pH in soil suspension (Ah-horizon of a Mollic Gleysol) and Mn²⁺ or Fe²⁺ concentrations in the equilibrium soil solution at different levels of glucose (0%, 0.5% and 1%) and MnO₂ (0%, 0.025%, 0.05% and 0.1%) or Fe₂O₃ (0%, 0.025%, 0.05% and 0.1%) were examined. It was found that the degree of Mn- and Fe-reduction in soil depends mainly on the presence and the amount of an easily decomposable carbon source and to a minor degree on the content of native or added forms of MnO_O2 or Fe₂O₃ in the soil. Theoretical relationships between the water soluble manganese and iron and the Eh and pH values have been verified, when the observed initial drop of Eh was eliminated. It was found that the water soluble manganese content was described best by the Mn₂O₃/Mn²⁺ redox system, and that of iron by the Fe₃ (OH)₃/Fe²⁺ system.