Coupled diffusion and oxidation of ferrous iron in soils. I. Kinetics of oxygenation of ferrous iron in soil suspension

The kinetics of oxidation of iron in an aqueous suspension of a thoroughly reduced low-humus tropical rice paddy soil were followed by measuring the extractable ferrous iron in the whole suspension and in the solution. Three-quarters of the initial ferrous iron was oxidized rapidly (first-order rate constant = 9.2 × 10^?5 s^?1). The subsequent reaction was slow (first-order rate constant = 9.4 × 10^?7 S^?1) and was not studied in detail. The pH fell from 6.6 to 4.9 over the course of the fast reaction. In further experiments the rate of oxidation was followed at constant pH values in the range 6.5 to 4.5. It was concluded that the oxidation of adsorbed iron was much faster than solution iron, and that the adsorbed iron was oxidized at a rate that was nearly independent of the pH. During the reaction some ferrous iron is adsorbed on the ferric hydroxide formed. The proportion of the remaining ferrous iron adsorbed on ferric hydroxide rather than the original exchange surfaces was high at pH > 6.0 and low at pH < 5.0. The rate of oxidation of the ferrous iron was similar whether it was adsorbed on exchange sites or on the ferric hydroxide formed. Since the rate of oxidation of the iron adsorbed on ferric hydroxide was very much slower than that on ferric hydroxide formed in the absence of soil, it is suggested that the rate in soil may be controlled by diffusion of oxygen to the adsorption sites.     

Visualisation of oxidizing power of rice roots and of possible participation of bacteria in iron deposition

The oxidizing power of rice roots was observed in narrow transparent root boxes containing different media. Plants precultivated in nutrient solution were embedded in semisolid agar medium to observe oxidation of ferrous iron cations and leuco methylene blue as well as solubilization of ferrous sulfide. In the presence of ferrous sulfate reddish brown coloration due to formation of ferric oxide/hydroxide was observed around the roots and on the root surface during one day of incubation. When agar medium blackened by ferrous sulfide was used, the root zone became transparent. Within a few hours leuco methylene blue was oxidized to methylene blue on and near the roots. Furthermore, seedlings were grown in agar medium containing ferrous sulfide inoculated with soil filtrate. Besides diffuse ferric iron precipitation, iron was also deposited on spherically shaped structures in the rhizosphere and near the agar surface as well as in slimy layers appearing on the root surface. The spherical structures and slimy layers were obviously bacterial colonies extending with time. As the roots grew old, parts of them turned black. In the rhizosphere, black spots occurred resembling colonies of sulfate-reducing bacteria. Rice was also grown in sand supplemented with nutrients and iron sulfide. While root growth was straight in agar, it was twisted in the sand medium. Again, heavy ferric iron deposition occurred on the root surface. On older root parts the lateral roots became blackish. The results suggest participation of bacteria in ferric iron deposition in the rhizosphere of rice.     

磷酸铁盐涂层: 控制黄铁矿氧化的新手段

A novel coating technique was develped for controlling pyrite oxidation .The technique involved leaching pyrite particles with a solution containing low concentrations of phosphate and hydrogen peroxide.During the leaching rpocess,the iron released from pyrite by hydrogen proxide was precipitated by phosphate as a ferric phosphate coating .This coating was shown to be able to effectively prevent pyirte from oxidation and it could be established at the expense of only surface portions of pyrite.The emergence of this technique could provide a unique potential route for abating acid mine draingage and reclaiming sulfide-containing degraded mining land.     

Pyrite oxidation in sediment samples from the German open‐cut brown coal mine Zwenkau: mineral formation and dissolution of silicates

Changes in mineral composition occurring in pyrite‐containing sediments under aerobic conditions are complex and not fully understood. The objective was to study the mineral formation and dissolution of silicates using ion activity product (IAP) calculations and x‐ray diffraction (XRD) on samples of different degrees of pyrite oxidation. Three sediment samples were obtained from the open‐cut brown coal mine of Zwenkau (Saxony, Germany) with low (ZL: 28 g kg^—1), medium (ZM: 67 g kg^—1) and high (ZH: 95 g kg^—1) pyrite contents. These samples were oxidized in the laboratory for 3, 20, 67, and 130 days to obtain four different degrees of pyrite oxidation for each sediment. Sequential batch experiments were carried out for each sediment and oxidation status. Additionally, cation exchange capacities were determined. XRD showed the formation of gypsum (all sediments), jarosite (ZM, ZH), and rozenite (ZH) with increasing pyrite oxidation. IAP calculations suggested an occurrence of gypsum in all samples, of schwertmannite in slightly (ZH) and moderately oxidized (ZM, ZL) samples, and of alunite in a moderately oxidized sample (ZL). The contents of feldspar (ZL), mica/illite (ZL, ZH), and kaolinite (ZH) decreased with increasing pyrite oxidation. The cation exchange capacities of the sediments decreased by 20 (ZH) to 70 mmol_c kg^—1 (ZM). The change in mineral phases with increasing oxidation status of the sediments also changed the activities of Al, Fe, and SO₄ in solution phases. The results obtained in this study suggested the usefulness of predictive models to estimate sediment and water acidification due to pyrite oxidation.     

Mechanistic Consideration of Zinc Ion Removal by Zero-Valent Iron

Mechanism of zinc iron removal by zero-valent iron was discussed through zinc removal responses to several operational conditions of a packed column reactor with zero-valent iron powder. The adsorption isotherm observed implied that a kind of chemisorption was responsible for zinc removal. Zinc removal by zero-valent iron was enhanced by dissolved oxygen and ferric ion addition. However, it was deteriorated under acidic pH. In addition, zinc adsorbed on zero-valent iron was eluted by a reducing agent such as citric acid, whereas the zinc was not eluted by diluted sulfuric acid. Consequently, the zinc removal mechanism by zero-valent iron was inferred to be as follows: Zero-valent iron was firstly corroded and oxidized into ferric ion by dissolved oxygen. The ferric ion was precipitated as iron hydroxide onto the surface of the zero-valent iron powder. Zinc ion was adsorbed on and/or coprecipitated with the iron hydroxide. The iron hydroxide was finally oxidized and transformed into iron oxides.     

Coupled diffusion and oxidation of ferrous iron in soils. II. A model of the diffusion and reaction of O2, Fe2+, H+ and HCO3− in soils and a sensitivity analysis of the model

Kinetic equations are developed for a system in which a column of reduced soil is exposed to oxygen at one end. The equations are combined in a simulation model in which they are solved by finite-difference methods. The model predicts the consequent diffusion of oxygen into the column; the diffusion of ferrous iron towards the oxidation zone; the rate of formation and concentration profile of the ferric hydroxide formed; and the diffusion by acid-base transfer of the acidity produced in the oxidation reaction. A sensitivity analysis of the model, in which runs were made for a wide range of input parameters, showed that for most combinations of parameters, in water-saturated soil, substantial amounts of iron are transferred towards the air-exposed surface, leading to a well-defined zone of ferric hydroxide accumulation. The profile of total iron in this zone is often banded. The pH in the zone falls by at least two units. A small amount of air-filled pore space increases the depth of the oxidation front dramatically. The model indicates that coupled iron oxidation and diffusion reactions, which are very widespread in natural soils, may be understood quantitatively.     

Residence times of alluvium in an east Texas stream as indicated by sediment color

The relationships between sediment production, storage, and transport in fluvial systems are complex and variable. Key issues in addressing these relationships are the residence times of sediment delivered to the channel, and the proportion derived from recent upland erosion as opposed to remobilized alluvium. The systematic changes in iron geochemistry often experienced by sediments deposited in an anaerobic environment, such as a stream channel or waterlogged floodplain, are used here as an indicator of residence time over contemporary time scales. In areas such as east Texas, where upland soils are high in iron oxide content, these changes are reflected in soil color. Alluvium with red, yellow, or brown colors indicating ferric (oxidized) iron and sufficient organic matter for reduction to occur indicates a short (<1 year) residence time. Redox features along root channels may indicate the residence time of oxidized material without organic matter. Alluvium with gley colors (Munsell chroma<3) indicates a longer residence time (>1 year). Sediments with the longest residence times in alluvial environments (≫1 year) will not oxidize on exposure to the atmosphere due to the loss of iron, while those with ferrous iron remaining will experience oxidation and color change on exposure. In Loco Bayou, Texas, these indicators of residence time are shown to be generally consistent with other field evidence of erosion and sedimentation. Further, the color indicators correctly indicate the residence time in several cases where the latter is known from field observations.     

Pyrite oxidation in a sediment sample of an open-cut brown coal mine: mineral formation,buffering of acidity and modeling of cations and sulfate

Secondary reactions occurring in pyrite‒containing sediments under aerobic conditions are complex and are not fully understood. Objectives were to (i) study the formation of secondary minerals using x‒ray diffraction (XRD) and ion activity product (IAP) calculations; (ii) to obtain a budget of acidity producing and consuming processes; and (iii) to study the performance of a chemical equilibrium model (including kinetic reactions) using sequential batch experiments with varying input solutions on samples of different pyrite oxidation states. A sediment sample from the open pit coal mine Garzweiler, Germany, was oxidised in the laboratory to obtain four different pyrite oxidation states. Sequential batch experiments were carried out using H₂O, 100 mM CaCl₂ and 10 mM NaOH as input solutions. A coupled equilibria model was used to describe the experiments. The model (PHREEQC) included inorganic complexation, redox reactions, precipitation/dissolution of sparingly soluble salts, multiple cation exchange and pyrite oxidation using a simple input function. IAP calculations and XRD showed the formation of large amounts of gypsum with increasing pyrite oxidation and for the highly oxidised sample also the formation of hydroniumjarosite. The budget of acidity consuming processes followed the order (i) release of Fe(III) into the solution phase (51% of produced acidity); (ii) Al release into solution and exchangeable phases (probably mainly due to silicate weathering, 22% of produced acidity); and (iii) CEC reducing processes (11% of produced acidity). Modeling of the sequential equilibration experiments with water and CaCl₂ gave satisfactory agreements between modeled and measured pH and sorption values, indicating that the main processes governing pH and ion sorption were quite well understood. However, model results of the alkaline additions at larger pyrite oxidation states differed considerably from the experimental results.     

Pyrite and siderite oxidation in swamp sediments

Differences in the processes of pyrite and siderite oxidation, in reclaimed swamp sediments of the Skjernå delta (Denmark), are described from sediment chemistry, mineralogy and pore water chemistry. Pyrite oxidation leads to extreme soil acidification, with pH dropping to about 2, the release of large amounts of weathering products to the pore water, and the precipitation ofiron oxides, jarosite and gypsum. Siderite oxidation results only in moderate soil acidification where the pH does not drop below 3.5, while part of the acidification is due to the oxidation of small amounts of sulphur compounds together with siderite. The release of weathering products to the pore water is limited and only iron oxide is precipitated. Calculations indicate that equilibrium with amorphous FeOOH, gypsum and amorphous Al(OH)₃ sets an upper limit to the Fe³⁺, SO₄ and Al concentrations in the pore water.     

Modellversuche zur Phosphatsorption von Unterwasserböden unter oxidierenden und reduzierenden Bedingungen

Model experiments on phosphate Sorption by river sediments under oxidizing and reducing conditions. During intensive reduction by sodium dithionite, phosphate sorbing river sediments often show a pronounced desorption of phosphate. Reoxidation by air causes an increase in phosphate sorption up to five times the original value, the height being linearly related to the ferric oxide content (Fe_d) of the sample. A possible explanation for this phenomenon is the oxidative precipitation of iron(III) oxides with high surface area being very active in phosphate adsorption.     

THE OXIDATION OF IRON SULPHIDES IN SOILS IN RELATION TO THE FORMATION OF ACID SULPHATE SOILS, AND OF OCHRE DEPOSITS IN FIELD DRAINS

Aerating pyritic soils causes acidification and the forrnation of acid sulphate soils, or cat-clay. The Oxidation of pyrite in soils is associated with the deposition in tile drains of a form of ochre quite distinct from that formed by the action of filamentous iron bacteria. Pyrite-derived ochre results from the action of Thiobacillus ferrooxidans, which, below pH 3.5–4.0, catalyses the Oxidation of Fe²⁺ and pyrite. In soils less acid than c. pH 4, pyrite oxidizes relatively slowly by chemical reactions to Fe²⁺ and SO²₄^?. Under these conditions iron enters the drains as Fe²⁺ and is there oxidized by T. ferrooicidans and deposited as hydrated ferric oxide. Once the soil becomes acid enough for T. ferrooxidans to multiply, the rate at which pyrite oxidizes increases several-fold, and at c. pH 3 iron appears in the drainage water in the ferric form. Liming seems to decrease the rate of Oxidation.     

Iron oxidation in different types of groundwater of Western Siberia

Background, aim, and scope  The groundwaters of Western Siberia contain high concentrations of iron, manganese, silicon, ammonium, and, in several cases, hydrogen sulfide, carbonic acids, and dissolved organic substances. Generally, the groundwaters of Western Siberia can be divided into two major types: one type with a relatively low concentration of humic substances and high hardness (water of A type) and a second type with a relatively low hardness and high concentration of humic substances (water of B type). For drinking water production, the waters of A type are mostly treated in the classical way by aeration followed by sand bed filtration. The waters of B type often show problems when treated for iron removal. A part of iron practically does not form the flocs or particles suitable for filtration or sedimentation. The aim of this work was to determine the oxidizability of Fe(II), to characterize the iron colloids, and to investigate the complexation of the iron ions with humic substances and the coagulation of the iron colloids in the presence of dissolved organic matter. Materials and methods  Water samples of the A and B types were taken from bore holes in Western Siberia (A type: in Tomsk and Tomsk region, B type: in Beliy Yar and Kargasok). Depth of sampling was about 200 m below surface. The oxidation of the groundwater samples by air oxygen and ozone was done in a bubble reactor consisting of a glass cylinder with a gas-inlet tube. To produce ozone, a compact ozone generator developed by Tomsk Polytechnic University was used. For the characterization of the colloids in the water of B type, the particle size distribution and the zeta potential were measured. To investigate the formation of complexes between iron and humic substances in the water of B type, size exclusion chromatography was used. The coagulation behavior of iron in the presence of dissolved organic substances was investigated at different pH values. The agglomerates were detected by measuring the optical density using a UV-Vis spectrometer. Results  Ozone showed, as expected, a faster oxidation of Fe(II) than air oxygen. The rate constants for Fe(II) oxidation were not much different for the waters of A and B types when the same oxidation process was used. However, the removal of iron after oxidation and filtration was higher in the water of A type than in the water of B type. No evidence for the formation of soluble complexes between iron and humic substances were found. In the water of A type, the coagulation process started at pH = 4.5 and accelerated with increasing pH value. In the water of B type, the coagulation of colloids occurred only at pH = 11 and higher. Discussion  The oxidation experiments indicated no major effect of dissolved organic carbon concentration on the kinetics of Fe(II) oxidation. In contrast to this, the humic substances showed a significant influence on the aggregation behavior of the iron hydroxide colloids. Due to the sorption of humic substances on the iron hydroxide colloids, they were highly stable in the pH range between 4.5 and 10. The particle size measurements confirmed the presence of small colloids in the water of B type. In contrast to this, the iron hydroxide colloids aggregated rapidly at pH = 11. Conclusions  The results showed a great influence of humic substances on the iron removal from groundwaters of Western Siberia with high organic content. The sorption of humic substances on the iron colloids does not obviously allow their coagulation and formation of flocs suitable for filtration or sedimentation. Recommendations and perspectives  By treatment of groundwaters containing high amounts of humic substances, some problems with the removal of iron are likely to occur. To increase the effectiveness of iron removal, the surface coating and pH-dependent charge effects should be taken into account by the selection and optimization of water treatment processes. The iron colloids coated by humic substances should be separated from the water phase by membrane filtration or by flocculation followed by filtration through different solid materials.     

Eisenkonkretionen in Graulehm-Sedimenten

Fe-concretions in Gray Loam-Sediments The large iron oxide-concretions (cm – dm in diameter) found in tertiary Gray Loam-Sediments (5309 Adendorf, FRG) are not relicts of fossil hydromorphic soils in the Eifel. In the sediments above brown coal layers rich in pyrite FeCO₃-concretions were formed. This was due to oxidation of sulfide to sulfate after carbonatization with CaCO₃ from loess at the surface while iron remained in the reduced stage. Later on the FeCO₃-concretions were transformed by oxidation to iron oxide-concretions.     

Differences in Iron, Manganese, and Phosphorus Binding in Freshwater Sediment Vegetated with Littorella Uniflora and Benthic Microalgae

Undisturbed sediment cores from an oligotrophic lake were percolated with artificial porewater to examine the effects of isoetid macrophytes,Littorella uniflora, and benthic microalgae on daily dynamics of sediment retention of phosphorus (P) by either iron (Fe) or manganese (Mn). Retention of Fe and Mn was observed due to oxidation processes mediated by oxygen release fromL. uniflora roots and benthic microalgae. Therefore increased retention of P was observed because of P precipitation with oxidized Fe- and Mn-compounds. During light periods, the ratio between Fe and P precipitation in the sediment was positively correlated with the P uptake byL. uniflora (p < 0.001, r² = 0.984). The atomic precipitation ratio between Fe and P was between I and 2. The ratio between oxidized Fe-compounds and Fe-bound phosphate in the sediment was positively correlated with the root density ofL. uniflora (p < 0 001. r² = 0.995). The ratio between Mn and P precipitation was higher (26) than the ratio between Fe and P. The role of benthic primary producers on P retention in freshwater littoral sediments is discussed.     

Ability of surfactant micelles to alter the physical location and reactivity of iron in oil-in-water emulsion

The purpose of this research was to determine how surfactant micelles influence iron partitioning and iron-promoted lipid oxidation in oil-in-water emulsions. Lipids containing ferric ions were used to produce oil-in-water emulsions, and continuous-phase iron concentrations in emulsions were measured as a function of varying continuous-phase polyoxyethylene 10-lauryl ether (Brij) concentrations. Continuous-phase iron concentrations increased with increasing surfactant micelle concentrations (0.1-2.0%) and storage time (1-7 days). At pH 3.0, the concentration of continuous-phase iron was higher than at pH 7.0. Similar trends in iron solubilization by Brij micelles were observed when either hexadecane or corn oil was used as the lipid phase. Lipid oxidation rates, as determined by the formation of lipid hydroperoxides and headspace hexanal, in corn oil-in-water emulsions containing iron decreased with increasing surfactant concentrations (0.5-2.0%). These results indicate that surfactant micelles could alter the physical location and prooxidant activity of iron in oil-in-water emulsions.     

Oxymyoglobin oxidation and membranal lipid peroxidation initiated by iron redox cycle.

Oxymyoglobin is the main pigment in muscle tissues, responsible for the bright red color of fresh meat. Oxidation of the heme iron from the ferrous to the ferric metmyoglobin produces the brownish color that consumers find undesirable in fresh meat. The aim of this study was to elucidate the mechanism of oxymyoglobin oxidation in muscle tissues by using a model system containing oxymyoglobin and muscle membranes oxidized by an iron redox cycle. Oxidation of oxymyoglobin was determined from the decrease in absorption of the solution measured by a spectrophotometer at 582 nm. Lipid peroxidation was determined by accumulation of TBARS and conjugated dienes. The higher rates of oxidation of oxymyoglobin (20 microM) and lipid oxidation were achieved by using ferric iron and ascorbic acid at concentrations of 50 and 200 microM, respectively. Increasing the concentration of ascorbic acid to 2000 microM switched its effect to antioxidative. Increasing the concentration of oxymyoglobin from 20 to 80 microM inhibited lipid peroxidation by >90% and partially prevented oxymyoglobin oxidation.     

Neutralization of atmospheric acid inputs in small spring catchments in the Frankenwald mountains,Germany

Investigations on soil and freshwater acidification are usually focused on well-aerated systems. This study deals with the role of reductive processes for the neutralization of acid soil solution within helocrene springs. Two toposequences consisting each of three profiles (forest soil, margin of fen, fen) were established to study the chemistry of the solid phase (soil pH, CEC, pedogenic Fe- and Al-oxides) and the soil solution in two small spring catchments on three dates during 1991 and 1992. Despite high acid inputs and acidified forest soils the pH of the spring outflow is near neutral, and the soil solid phases of the spring fens are not acidified. The results support the following hypothesis: Aluminum with its corresponding anion sulfate is leached with the soil solution into the water-saturated fens. Dissimilatory iron and sulfate reduction take place within the fen and generate alkalinity. Reduced iron either reacts with sulfide to form pyrite or migrates within the fen profile and precipitates in the uppermost, oxic horizons, consuming part of the generated alkalinity. Due to the higher pH values in the fens the incoming aluminum precipitates releasing acidity. The alkalinity generated exceeds the amount of acidity released by oxidation and precipitation of iron and the precipitation of aluminum. A balance of alkalinity consuming and alkalinity generating processes based on solid phases showed that iron and sulfate reduction can account for at least 67% of the neutralization of acidity entering the fen of one of the catchments. Due to shorter water retention times and higher discharge these processes are of minor importance in the other catchment.     

The role of iron and the factors affecting off-color development of polyphenols

Iron deficiency affects over two billion people worldwide (Lotfi, M.; Venkatesh Mannar, M. G.; Merx, R. J.; Naber-van den Heuvel, P. Micronutrient Fortification of Foods: Current Practices, Research,and Opportunities; Micronutrient Initiative: Ottawa, Ontario, Canada, 1996). However, fortifying foods with highly bioavailable iron is technically challenging because of off-color and off-flavor development, catalytic degradation of vitamins, and oxidation of lipids. The role of highly bioavailable iron in the off-color development of foods and beverages is not well-understood. The goal of this research was to examine the interaction of iron with simple phenolics and polyphenols. Factors that may affect off-color development, such as pH, oxygen, temperature, and reducing and chelating agents, were evaluated as a model for food products. Our results demonstrated that the iron that reacts with the simple phenolic, catechol, to develop off-color must be in the oxidized state, and the iron is reduced in the presence of catechol. Because this is an oxidation/reduction reaction, the redox potential of all of the components is critical to the color development. Ferrous iron sources with low redox potentials and ferric iron sources with high redox potentials caused off-color development with catechol. Only polyphenols that contain ortho-hydroxyl groups cause off-color development with iron. All of the factors tested affect off-color development and redox potential of the system. Low pH, low oxygen, high temperature, and the presence of reducing and chelating agents inhibited off-color development. To confirm the model, foods that contained these polyphenols were evaluated for off-color development when iron was added. The foods tested reacted similarly to the models of polyphenols with iron. Off-color development was caused by oxidation-reduction interactions between ferric iron and polyphenols that contained ortho-dihydroxyl groups. Ferrous iron needed to be oxidized to participate in off-color development. In addition, methods identified in the models to prevent off-color development were effective in most of the food products examined. Using the ferrous form of iron and maintaining it in its reduced form by lowering pH, removing oxygen, and including reducing agents, it was possible to fortify foods with highly bioavailable iron.     

Secondary minerals from extrapedogenic per latus acidic weathering environments at geomorphic edges, Eastern Nebraska, USA

Acidic weathering of the sulfidic Upper Cretaceous Carlile and Pierre Shales in Nebraska has led to the precipitation of the Al sulfate–hydroxide minerals aluminite, alunite, “basaluminite”/felsöbányaite (e.g.,), the aluminum hydroxides gibbsite and bayerite, and the rare Al phosphate hydroxide vashegyite. Kaolinite has also been produced as a result of this acidic weathering. These minerals do not appear as neoformed constituents in any extant soils in the region, and their existence underscores the ability of pyrite oxidation to produce major changes in mineralogy on a Holocene to Recent time scale. Jarosite, hydronium jarosite, gypsum, halotrichite, and melanterite also appear as secondary minerals in the weathered shales. Acidic weathering and the formation of new minerals is extrapedogenic because it occurs well below the limit of modern soil sola. These processes also occur at the edges of major landscape elements and can be considered to have a strong lateral component processes, making them “per latus” processes in our usage.     

Natural “amorphous” ferric hydroxide

Rusty ferruginous precipitates deposited from soil-borne waters (in drainage ditches, from springs) at various localities, contain a ferric hydroxide rich in carbon and adsorbed water. It has up to 75% dithionite soluble Fe₂O₃, of which between 90 and 100% is oxalate soluble IR spectrograms do not show Fe-OH features in the OH stretching and bending range. X-ray diffraction reveals very broad lines at about 2.5 and 1.5 Å and somewhat sharper lines at 2.22, 1.97 and 1.71 Å, which are characteristic of ferrihydrite (name proposed by Chukhrov et al., 1972). These deposits are found in areas where water has percolated through acid soils rich in low molecular weight organic compounds. Furthermore, as similar material could be prepared in the laboratory by bacterial or H₂O₂ oxidation of ferric citrate solutions, it was concluded that the natural substance is formed by microbial decomposition of soluble iron—organic complexes. Transformation experiments suggest that aging under conditions corresponding to a humid temperate climate causes conversion to goethite. This aging process is greatly retarded by organic and other compounds retained by the hydroxide. No evidence of hematite formation could be found after 2 weeks at 70°C.