The presence of Al hydroxy species in solution during the synthesis of lepidocrocite had been previously found to influence the reaction towards goethite formation. However, under certain conditions, which are not unrealistic in terms of the natural soil environment, this influence does not occur, and Al appears to substitute for Fe(III) in the lepidocrocite structure. This substitution causes the unit-cell dimensions to decrease along the “a” direction and to increase along the “b.” From the differential line broadening of X-ray powder diffraction peaks, the incorporation of Al was found to inhibit crystal growth preferentially in the b-axis direction, the hkl peaks being more broadened the higher the value of k relative to h and l. Al-substituted lepidocrocites have been suggested to occur in soils, and although they can be synthesized under conditions approaching those expected in soils, it is considered that their formation in nature is unlikely or restricted to unusual environments.

The different types of iron oxide phases associated with the surfaces of two suites of kaolins from Georgia, U.S.A., and from the Southwest Peninsula of England, have been identified using electron spin resonance (ESR) spectroscopy combined with magnetic-filtration, thermal, and chemical treatments. It has been shown that the English kaolins are coated with a lepidocrocitelike phase, which is readily removed by de Endredy's method of deferrification, while the Georgia kaolins are coated with a hematite- or goethitelike phase, which is not removed by this treatment. Throughout the course of this study, the effects of the various physical and chemical treatments on the brightness values of the kaolins were examined.

Feroxyhite (δ′-FeOOH) in association with goethite and lepidocrocite was found as a dominant mineral in some rusty precipitates from Finland. These precipitates formed in the interstices of sand grains from rapidly flowing, Fe(II)-containing water which was very quickly oxidized as it flowed through the sediment. The mineral is distinguished from other FeOOH forms and from ferrihydrite mainly by its X-ray powder diffractogram. Further characteristics are an acicular morphology (possibly thin, rolled plates), an internal magnetic field at 4°K of ∼510 kOe, Fe-OH stretching bands at ∼2900 cm−1 and Fe-OH bending bands at 1110, 920, 790, and 670 cm−1, and an oxalate solubility between ferrihydrite and goethite or lepidocrocite. Feroxyhites with very similar properties were synthesized by oxidation of an Fe(II) solution with H2O2 at a pH between 5 and 8.

Lepidocrocite was identified associated with mica particles and in the clay fraction of two well-drained Ontario soils developed on a granite and a granite-gneiss. The occurrence of lepidocrocite is rare outside the tropics and there are no reports on its existence in well-drained soils.

The influence of Al on the products formed by aerial oxidation at pH 5.5-7 and 20°C of Fe(II) chloride, sulfate and carbonate solutions, was examined. In all cases Al at levels Al/Al + Fe = 0.09−0.30 inhibited the formation of y phases (lepidocrocite and maghemite) in favor of goethite under conditions where, in the absence of Al, these y phases formed. The influence of Al in these laboratory studies was supported by field observations.

At higher levels of Al, ferrihydrite formation was favored. This effect of Al was seen to be the result of a slowing down in the hydrolysis/oxidation rate of the Fe(II) system.

The presence of Al not only changed the direction of mineral formation, but also caused the formation of Al substitued goethites which resembled in particle size and morphology the natural aluminiferous goethite extracted from a soil.

The dissolution of synthetic magnetite, maghemite, hematite, goethite, lepidocrocite, and akaganeite was faster in HCl than in HClO4. In the presence of H+, the Cl− ion increased the dissolution rate, but the ClO4− ion had no effect, suggesting that the formation of Fe-Cl surface complexes assists dissolution. The effect of temperature on the initial dissolution rate can be described by the Arrhenius equation, with dissolution rates in the order: lepidocrocite > magnetite > akaganeite > maghemite > hematite > goethite. Activation energies and frequency factors for these minerals are 20.0, 19.0, 16.0, 20.3, 20.9, 22.5 kcal/mole and 5.8 × 1011, 1.8 × 1010, 7.4 × 107, 5.1 × 1010, 2.1 × 1010, 3.0 × 1011 g Fe dissolved/m2/hr, respectively. The complete dissolution of magnetite, maghemite, hematite, and goethite is well described by the cube-root law, whereas that of lepidocrocite is not.

The influence of Mn2+ on the formation of Fe oxides at pHs of 6.0 and 8.0 and varying Mn/Fe molar ratios (0, 0.1, 1.0, and 10.0) in the FeCl2-NH4OH and FeSO4-NH4OH systems was studied by X-ray powder diffraction (XRD), infrared absorption, transmission electron microscopic, and chemical analyses. In the absence of Mn2+, lepidocrocite (γ-FeOOH) and maghemite (γ-Fe2O3) were the crystalline species formed at pHs of 6.0 and 8.0, respectively, in the FeCl2 system, whereas lepidocrocite and goethite (α-FeOOH) and lepidocrocite were the crystalline species formed at pHs of 6.0 and 8.0, respectively, in the FeSO4 system. The amount of Mn coprecipitated with Fe (as much as 8.1 mole % in the FeCl2 system and 15.0 mole % in the FeSO4 system) increased as the initial solution Mn/Fe molar ratio increased from 0 to 10.0, resulting in the perturbation of the crystallization processes of the hydrolytic products of Fe formed. At pH 6.0, the perturbation led to the formation of poorly ordered lepidocrocite, as reflected in the increasing broadening of its characteristic peaks in the XRD patterns. At pH 8.0, poorly ordered iepidocrocite and a honessite-like mineral (Mn-Fe-SO4-H2O) formed in the FeCl2 and FeSO4 systems, respectively.

Lepidocrocite samples, γ-FeOOH, containing 0–10 mole % Al-for-Fe substitution were synthesized at 15°C and pH 8 by oxidizing mixed FeCl2-AlCl3 solutions. The unit-cell parameters a, b, and c were measured from step-counted X-ray powder diffractograms using seven lines and Si as an internal standard. With increasing Al substitution from 0 to 10 mole % the unit-cell edge lengths a, b, and c decreased regularly by 0.3, 0.8, and 0.6%, respectively. Furthermore, the crystals became smaller, but gained in thermal stability. Decrease in crystal size parallel to the y axis led to a significant increase of the OH-stretch vibration and a decrease of the out-of-plane OH-bending vibration due to a weakening of the hydrogen bond between the zig-zag layers in the structure.

The rate of dissolution of akaganéite in HCl increased with time over the bulk of the reaction leading to a sigmoid dissolution vs. time curve. The bulk of the dissolution of lepidocrocite could be described by the cube root law. Transmission electron microscopy examination of partly dissolved crystals of akaganéite showed that acid attack proceeded mainly along the [001] direction. Initially, the tapered ends of the crystals became squared, and as dissolution continued the lengths of the crystals decreased steadily. At the same time, the crystals were gradually hollowed out. Acid attack was most pronounced at the edges of the crystals of lepidocrocite and appeared to involve a disruption of the hydrogen bonds that link the sheets of octahedra making up the structure. Defects also acted as sites for preferential acid attack. Dissolution of multi-domainic crystals involved preferential attack along the domain boundaries, as well as at the edges of the crystals. Single-domain crystals were well developed, but appeared to contain internal imperfections, which promoted the formation of holes on the otherwise unreactive (010) faces.

The formation of fine-grained magnetite (~0.1 μm) at pH 7 and 25°C from aeration of Fe(II) chloride solutions is presented. The magnetite converted at 105°C to maghemite with poorly developed superstructure lines. Under the experimental conditions employed, as the initial [Cl]/[Fe] ratio was increased from the stoichiometric value of 2, the final product contained increasing amounts of lepidocrocite. The degree of crystallinity of this phase, as measured by the width at half height of the 020 X-ray diffraction peak, also increased with this ratio. The hydrolysis rate (base consumption to maintain pH) showed a plateau whose position and extent changed with the initial [Cl]/[Fe] ratio. Through this plateau region the Eh decreased to a minimum value the position of which was directly related to the [Cl]/[Fe] value. The formation of lepidocrocite rather than magnetite is likely due to the high [Cl] where there would be increased difficulty for neighboring OH to condense and eliminate H2O. The formation of Fe-O-Fe bonds in this condensation would be impeded by Cl substitution for OH either in the first formed green rust stage or during its oxidation.

Ferrous or ferric Perchlorate, 0.01 M, was reacted with calcite in stirred aqueous suspensions which were bubbled vigorously with an oxidizing purge gas. Two and three equivalents of CaCO3 were dissolved per mole of Fe2+ and Fe3+ neutralized, respectively. With Fe(ClO4)2, the crystalline Fe oxide products partially coated the calcite surface. The dominant products were lepidocrocite and goethite when the purge gas was air or 20% CO2 (balance air), respectively. After reaction with Fe2+ the edges and corners of the calcite crystals were generally rounded and the faces were non-uniformly pitted; however, after reaction with Fe3+, a mosaic pattern with distinct ridges and channels was evident on the calcite. These ridges were somewhat pitted, but distinct stepped dislocations were present leading to a featureless and generally flat channel floor. When the calcite was separated from the Fe solution by a semi-permeable membrane, precipitation occurred predominantly on the calcite side and on the Fe side of the membrane in the Fe2+ and Fe3+ systems, respectively.

Fe oxyhydroxides precipitated from the Fe(ClO4)3 and Fe(ClO4)2 solutions by different mechanisms. In the Fe(ClO4)3 system, although the initial reaction may have been at the calcite surface, the bulk of the poorly crystalline ferrihydrite was formed by hydrolysis of Fe polymers in suspension. Neutralization occurred by the reaction with basic products of a surface-controlled dissolution of calcite, rather than by a direct reaction of acidic polymers with the calcite surface. In the Fe(ClO4)2 system, lepidocrocite or goethite formed by the partial hydrolysis of Fe2+ or Fe3+ by reaction with calcite or the basic products of calcite dissolution and subsequent precipitation of simple Fe species on existing FeOOH nuclei.

During photochemical dissolution of goethite in acid/oxalate solution, Fe3+, Fe2+, and CO2 were released and towards the end of the reaction ferrous oxalate precipitated. The dissolution process involved an initial slow stage followed by a much faster reaction. The slow stage was eliminated by addition of 20 ppm Fe2+ to the system at the start of the reaction. The presence of this Fe2+ did not accelerate the secondary dissolution process. Both protons and oxalate ions appear to have been involved in the dissolution process. Dissolution was accelerated by an increase in oxalate concentration (from 0.0025 to 0.025 M) in the system and also depended on pH, reaching a maximum rate at pH 2.6. Highly substituted (15.9 mole % Al) goethite dissolved more slowly per unit area than unsubstituted goethite. Lepidocrocite (γ-FeOOH) dissolved faster than goethite. The first stage of the dissolution process probably proceeded by slow release of Fe3+ through complexation with oxalate adsorbed on the goethite surface. The faster, secondary step appears to have been a reductive dissolution reaction involving adsorbed ferrous oxalate.

Iron salts react readily with calcite in oxidizing calcareous environments to produce solid phase Fe-oxides. These reactions represent important processes in aqueous, geologic, and pedogenic environments. In the present investigation, Fe-oxides were precipitated from Fe(ClO4)2 solutions on undisturbed calcite grains in aqueous suspension. In this way it was possible to investigate the sequence of events in the crystallization process. Following an initial precipitation on the calcite grains, a period of slow growth of lepidocrocite was noted wherein 4-μm euhedral platelets formed with uniform orientation perpendicular to the calcite surface. The slow growth and highly crystalline nature of the Fe-oxide product may be partially due to the diffusion barrier formed by the growing oxide crystal mass which influenced rate of movement of HCO3− to the dissolved Fe phase and Fe ions and H+ towards the calcite surface. Upon continued aging, the supernate became noticeably opaque. As the suspended nuclei settled, new surfaces for crystal growth were provided which resulted in somewhat less crystalline lepidocrocite and goethite.

Diffractograms of lepidocrocites formed from the oxidation of Fe(II) chloride solutions at pH 7 and 25°C showed differential line broadening with (0k0) reflections being much sharper than (hk0) or (hkl). As the initial [Cl]/[Fe] ratio was increased from 2, crystallinity increased in all axial directions, as defined by the width at half height of diffraction peaks. At [Cl]/[Fe] ratios greater than ~8, the crystallinity did not increase further, and for reflections involving the a-axis direction, it appeared to decrease. Increased [Cl]/[Fe] ratios changed the rate of the oxidation/hydrolysis reactions. These variations reflect changes in the stability and/or composition of the intermediate green rust phase, (Fe(II)Fe(III) hydroxychloride) in the high [Cl] environment. The influence of the [Cl]/[Fe] ratio was related to the experimental conditions employed, especially where they influenced the rate of oxidation.

The rate of Fe(II) oxidation at a constant rate of oxygen supply in the presence of citrate was measured at pH 6.0 at various citrate/Fe(II) molar ratios at 23.5°C in 0.01 M ferrous Perchlorate system. The kinetics followed a first-order reaction with respect to Fe(II) concentration at constant pH (6.0) and aeration (5 ml/min). The rate constant decreased exponentially from 41.3 × 10-4 to 7.6 × 10-4/min with an increase in the citrate/Fe(II) molar ratio from 0 to 0.1.

The nature of the hydrolytic products formed after 120 min of oxidation was arrived at by X-ray powder diffraction (XRD), infrared spectrometry (IR), and transmission electron microscopic (TEM) analyses. In the absence of citrate, goethite (α-FeOOH) and poorly crystalline lepidocrocite (γ-FeOOH) were the oxidation products formed at pH 6.0. The formation of lepidocrocite was promoted at the expense of goethite at citrate/Fe(II) molar ratios of 0.0005 to 0.005. The formation of lepidocrocite was especially pronounced at a citrate/Fe(II) molar ratio of 0.001, as observed from the width at half height (WHH) and the area of the 020 XRD peak of lepidocrocite. At a citrate/Fe(II) molar ratio of 0.01, however, the crystallization was perturbed resulting in the formation of noncrystalline Fe oxides, and no precipitate was observed at a citrate/Fe molar ratio of 0.1. The strong complexation of Fe(II) with citrate retarded the kinetics of Fe(II) oxidation and the formation and hydrolysis of Fe(III). The complexation, electrostatic, and steric effects of the coexisting citrate anions in solution apparently influenced the oxygen coordination and the way by which the double rows of edge-sharing Fe(O,OH)6 octahedra linked during crystallization, resulting in the formation of lepidocrocite.

Well-crystallized ferrihydrite as indicated by its X-ray powder diffraction pattern and low solubility in acidified oxalate (Feo/Fet = 0.27) was formed by the oxidation of FeCl2 solution containing Si/Fe = 18 × 10−3. The crystallinity of ferrihydrites formed from the solutions containing Si/Fe > 18 × 10−3 was lowered as indicated by weaker and broader XRD lines and increased oxalate solubility. Ferrihydrites formed in the presence of silica did not give the differential thermal analysis exothermic peak between 350° and 450°C that is found for ferrihydrites prepared from the hydrolysis of Fe(III) salts. The transformation of ferrihydrite (formed at Si/Fe = 18 × 10−3) to hematite was inhibited by the presence of 1.48% SiO2 in the oxidation products.

Pillared structures with an interlayer opening of ∼0.3 nm were obtained after successive heat treatments of the PILC precursor in reducing and oxidizing conditions. This precursor was prepared by reacting a Na+-montmorillonite with an intercalant containing Al and Fe oxo-hydroxides (Al/Fe = 1). Powder X-ray diffraction, elemental analysis, 57Fe Mössbauer spectroscopy, catalytic activity measurements and surface area data were used to characterize the samples. On the basis of Mössbauer spectra taken at temperatures between 4.2 and 300 K, it is deduced that oxidizing steps produce Al substituted maghemite which converts into Al substituted magnetite upon reducing heat treatment. Firing the precursor in oxidizing atmosphere forms pillars of few nm in diameter. However, heating under reducing conditions yields pillars of smaller diameter. This later behaviour is maintained even after reheating the material in oxidizing atmosphere. From the temperature dependence of Mössbauer spectra it is deduced that the diameter of the Fe oxide particles in the pillars is smaller than 10 nm.

The effect of phosphate on the formation of Fe oxides from Fe(II) salts is important because phosphate is a ubiquitous anion in natural environments. For this reason, the products formed by oxidation of phosphate-containing Fe(II)SO4 solutions neutralized with bicarbonate were characterized. The rate of oxidation of Fe(II) increased with increasing P/Fe atomic ratio to 0.2 in the initial solution. Goethite (α-FeOOH) or lepidocrocite (γ-FeOOH) or both were produced and identified by powder X-ray diffraction (XRD). The ratio between lepidocrocite and goethite increased with increasing P/Fe. In the 5–8.5 pH range, the formation of goethite predominated at P/Fe < 0.005, but only lepidocrocite was detected by XRD for P/Fe > 0.02. Thus, phosphate favors lepidocrocite formation because lepidocrocite has (1) a layered structure (like its precursor green rust), and (2) a structure less dense than that of goethite, thereby requiring less complete removal of the green-rust interlayer phosphate to form. The lepidocrocite crystals were platy, with prominent {010} faces and the thickness of the plates decreased with increasing P/Fe from >25 nm for P/Fe < 0.005 to <5 nm for P/Fe > 0.1. The solubility of lepidocrocite in acid oxalate was nearly complete for P/Fe > 0.03. The lepidocrocite contained occluded phosphate, i.e., phosphate that could not be desorbed by alkali treatment. The decrease in the b unit-cell length with increasing P/Fe suggests that lepidocrocite may contain structural P.