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.

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.

Iron impurities in the Hohen Hagen nontronite (NG-1) were identified as maghemite and goethite. The phase identified as maghemite was magnetically ordered at both room temperature and 87 K, with hyperfine magnetic fields of 48.6 and 50.7 tesla, respectively. Due to the magnetic properties of this phase, it was easily separated from aqueous dispersions of the clay using a hand magnet. X-ray powder diffraction analysis revealed maghemite, quartz, and phyllosilicate in the magnetically separated phase. The impurity identified as goethite remained in the non-magnetic <2-μm fraction of the clay, displayed magnetic order only at 87 K (47.44 tesla hyperfine field), and accounted for about 8% of the total area of the Mössbauer spectrum.

X-ray powder diffraction (XRD), transmission electron microscopy, infrared spectroscopy, differential thermal analysis, and surface area (BET) measurements were employed to investigate the transformation of microcrystalline maghemite to hematite. At 500°C pure maghemite was completely altered to hematite in 3 hr, whereas maghemites containing small amounts (≤1%) of Co, Ni, Zn, Cu, Mn, Al, V, and Cr required much longer heating times. The maghemite-to-hematite transformation temperature varied from 540° to 650°C. XRD line widths suggest that each particle of maghemite and hematite may have been a mosaic of many independent, coherently diffracting crystals. The transformation of maghemite to hematite at 650°C was accompanied by a reduction in surface area due to sintering of particles.

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.

Synthetic, relatively well-crystallized aluminum-substituted maghemite samples, γ-(Aly·Fe1−y)2O3, with y = 0, 0.032, 0.058, 0.084, 0.106 and 0.151 have been studied by X-ray diffraction and zero-field Mössbauer spectroscopy in the range 8 K to 475 K, and also with an external field of 60 kOe at 4.2 K and 275 K. It was found that there are two different converging models for fitting the zero-field spectra of the maghemites with a superposition of two Lorentzian-shaped sextets, both resulting in inconsistent values for the hyperfine fields (Hhf) and/or the center shifts (δ) of the tetrahedral (A) and octahedral (B) ferric ions. From the applied-field measurements it is concluded that there is a constant difference of 0.12 ± 0.01 mm/s between δB and δA, regardless of the Al content. For the Al-free sample the center shifts are found as: δA = 0.370 mm/s and δB = 0.491 mm/s at 4.2 K and δA = 0.233 mm/s and δB = 0.357 mm/s at 275 K (relative to metallic iron), with an estimated error of 0.005 mm/s. Both δA and δB are observed to decrease with increasing Al concentration. The effective hyperfine fields for the non-substituted maghemite sample are: Heff,A = 575 kOe and Heff,B = 471 kOe at 4.2 K and Heff,A = 562 kOe and Heff,B = 449 kOe at 275 K, with an error of 1 kOe. The B-site hyperfine field remains approximately constant with Al substitution, while for the A site a slight decrease with increasing Al content was observed.

Many soils developed from volcanic rocks in southern Brazil exhibit spontaneous magnetization caused by the presence of fine-grained maghemite (γ-Fe2O3), but few attempts were made to quantify or characterize this important soil component. To that end, clays were separated from freely drained soils derived from acid (≥63% SiO2), intermediate (54–62% SiO2), and basic (≤53% SiO2) igneous rocks produced by the Paraná flood volcanism. The sample set included soils with a wide range of pedogenic development on different landscape positions. The Fe oxide mineralogy of these samples was examined by using a combination of selective dissolution, magnetic susceptibility, and X-ray diffraction (XRD) techniques. Hematite and maghemite were the primary Fe oxides in mature soils (Oxisols, Ultisols, and Alfisols) developed from basic rocks; whereas goethite was dominant in all other soils, especially those formed from acid-intermediate rocks. The association of maghemite with basic rock materials suggests that it was primarily formed by oxidation of lithogenic magnetite. A strong, positive correlation (R2 = 0.89) was obtained between mass specific magnetic susceptibility (χ) of the clay fractions and maghemite contents estimated by XRD. Either method could be used for quantitative analyses, but χ was more sensitive than XRD at low maghemite concentrations (<2 wt. %). The clay-sized maghem-ites were superparamagnetic with an estimated value for the mass specific magnetic susceptibility (χlf) value of 91,000 × 10−8 m3 kg−1 and frequency dependent variations of 10–15%. The maghemites also had low unit cell constants, which, if attributed entirely to replacement of Fe by Al, would correlate with Al substitutions in the range of 5–16 mole %. Selective dissolution of the soil maghemites was achieved by treatment of Fe oxide concentrates with 1.8 M H2SO4 at 75°C for 2 h.

Infrared (IR) spectroscopy, in combination with magnetic methods, was used to study the thermally induced transformation of synthetic lepidocrocite (γ-FeOOH) to maghemite (γ-Fe2O3). Magnetic analyses showed that the thermal conversion began at about 175°C with the formation of superparamagnetic maghemite clusters. The overall structural transformation to ferrimagnetic γ-Fe2O3 occurred at 200°C and was complete around 300°C. At higher temperatures, the maghemite converted into hematite (α-Fe2O3). Observation of the transformation from γ-FeOOH to γ-Fe2O3 using variable-temperature IR spectroscopy indicated that dehydroxilation on a molecular level was initiated between 145°C and 155°C. The lag time between the onset of the breaking of OH bonds and the release of H2O from lepidocrocite around 175°C can be explained by diffusive processes. Overall dehydroxilation and the subsequent breakdown of the lepidocrocite structure was complete below 219°C. The comparison of the magnetic and IR data provides evidence that the dehydroxilation may precede the structural conversion to maghemite.

A dusky red Oxisol forming on a tholeiitic basalt is found to contain varying proportion of aluminous hematite (Hm) and titanoaluminous maghemite (Mh) in the different size fractions. Maghemite is the main iron oxide in the sand and silt fractions whereas Hm is dominant in the clay fraction, together with gibbsite (Gb), kaolinite (Ka), rutile (Rt) (and probably anatase, An) and Mh. Maghemite is also the major oxide mineral in the magnetic separates of soil fractions (sand, about 65% of the relative Mössbauer spectral area; silt, 60%). Hematite (sand, 30%; silt, 15%) and ilmenite (Im) (sand, 5%; silt, 16%) are also significantly present in the magnetic extract. Accessory minerals are Rt and An. No magnetite (Mt) was detected in any soil fraction. Sand- and silt-size Mh have similar nature (a 0= 0.8319 ± 0.0005 nm; about 8 mol% of Al substitution; saturation magnetization of 49 J T−1 kg−1), and certainly a common origin. Lattice parameters of clay-Mh are more difficult to deduce, as magnetic separation was ineffective in removing nonmagnetic phases. Al content in Hm varies from 14 mol% (clay and silt) to 20 mol% (sand). The proposed cation distribution on the spinel sites of the sand-size Mh is:

$[{\text{Fe}}_{0.92}{\text{Al}}_{0.08}]\hspace{0.17em}\left\{{\text{Fe}}_{1.43}{\text{Ti}}_{0.18}\hspace{0.17em}{\square }_{0.39}\right\}{\text{O}}_4$

(◻ = vacancy, [ ] = tetrahedral sites and { } = octahedral sites), with a corresponding molar mass of 208.8 g mol−1. The predicted magnetization based on this formula is σ ≅ 68 J T−1 kg−1, assuming collinear spin arrangement. The large discrepancy with the experimentally determined magnetization is discussed.

Synthetic aluminum-substituted maghemite samples, γ-(Fe1-xAlx)2O3, have been prepared by thermal decomposition of Al-lepidocrocite (γ-Fe1-xAlxOOH), with × = 0, 0.04, 0.06, 0.14 and 0.18. The particles are needle-shaped and the mean crystallite diameter along the [311] crystallographic direction was found to be between 2.0 and 5.0 nm. Mössbauer spectra were collected at 6 K and from 80 K up to 475 K at steps of 25 K. In a wide range of temperatures the spectra of the non-substituted sample consist of a superposition of a broad sextet and a superparamagnetic doublet, whereas for the Al-maghemites this range is much smaller. From the temperature variation of the fractional doublet area two different parameters were defined: the temperature corresponding to a 50/50 doublet-sextet spectrum (T1/2), and the temperature below which the doublet ceases to exist (T0). These two parameters (T1/2 and T0) decrease from 390 K and 92 K (Al-free sample), to 118 K and 64 K (4 mole % Al) and to 100 K and 48 K (18 mole % Al), respectively. The average hyperfine fields at 6 K undergo a steep drop in going from the Al-free sample (Hhf = 506 kOe) to the sample with 4 mole % Al (Hhf = 498 kOe), but for higher substitutions the effect is much smaller. The A- and B-site quadrupole splittings, obtained from the data between 220 K and 475 K, were found as: ΔEQ,A = 0.86 ± 0.04 mm/s and ΔEQ,B = 0.65 ± 0.04 mm/s for the 4 mole % Al sample. The characteristic Mössbauer temperature, determined from the temperature dependence of the average isomer shift, was found to be in the range of 500–600 K.

Fe(II) and Fe(III) in various proportions were coprecipitated by NH3 at pH ≈ 11. The Fe(II)/Fe(III) ratio (x) was varied from 0.10 to 0.50. After stabilization by aging at pH ≃ 8 in anaerobic conditions, hydrous precipitates were characterized by electron microscopy, Mössbauer spectroscopy, and kinetics of dissolution in acidic medium. At any x value, all stable products exhibited the structure of (oxidized) magnetite. For x ≤ 0.30, two distinct species were coexisting: the one (“m”) was made up of ca. 4nm-sized particles with a low Fe(II) content (Fe(II)/Fe(III) ≈ 0.07), and the other (“M”) consisted of particles of larger, more or less distributed sizes, and composition Fe(II)/Fe(III) ≈ 0.33; “M” increased relative amount with increasing x. For x ≥ 0.35, “M” was the only constituent and its Fe(II)/Fe(III) ratio was equal to x. “M” is identified with (nonstoichiometric) magnetite, whereas “m” is likely to be an oxyhydroxide. Mechanisms of formation are discussed, and a phase diagram is proposed which schematizes the evolution of the coprecipitation products with x and with time. Addition of Fe(II) after the precipitation of Fe(III), instead of coprecipitation, yielded very similar results.

Submicron-sized (~3–60 nm) powders of Al-substituted magnetite were synthesized in the laboratory by precipitation methods by mixing appropriate molar volumes FeCl2, FeCl3 and AlCl3 solutions and precipitating with 20% NH4OH. Precipitates were dialyzed for 48 hr to remove excess salts and then freeze-dried. The nominal Al mole fractions [Als = Al/(Al + Fe)] in the initial precipitate ranged from 0.001 to 0.42. Portions of the resulting powders were heated sequentially in air at 400° and 500°C. Powders were examined using X-ray diffraction (XRD), transmission electron microscopy (TEM), and visible and near-IR reflectance spectroscopy. Solubilities were determined in ammonium oxalate (pH = 3) and dithionite-citrate-bicarbonate (DCB) solutions. As determined by XRD, the mineralogy of precipitated powder samples was predominantly magnetite. Powders having Als > 0.20 contained minor goethite and a poorly crystalline iron oxide phase (ferrihydrite?), and powders having Als > 0.25 also contained gibbsite. The color of the magnetites was black throughout the range of Al-substitution. Powders heated to 400°C were reddish brown; Munsell colors ranged from 5R 2/2 to 10R 3/4 for Als from 0.1–41.5%, respectively. By XRD, these powders were maghemite, but hematite was also detected by Mössbauer spectroscopy. XRD and Mössbauer data indicate powders heated to 500°C are hematite; their Munsell colors are not noticeably different from the corresponding 400°C samples. Mean crystallite dimensions (MCDs) of the magnetite powders increase with the Al mole fraction from ~10 nm for Als = 0.001% to a maximum value of 35 nm for Als = 0.15 and decrease slightly with further increasing Al substitution. Heating magnetite powders to 400°C did not change the MCDs significantly. Heating to 500°C resulted in hematites having MCDs larger than those for corresponding precursor magnetites for Als < 0.10. The opposite is true for hematites derived from magnetites having Als > 0.10. For hematite powders with Als > 0.05, MCD decreased with increasing Al-substitution. Solubilities of powders in oxalate solutions were independent of Al content and decreased in the order unheated samples (mostly magnetite) >400°C-heated samples (maghemite + hematite) >500°C-heated samples (hematite). All powders dissolved completely in DCB. The low crystallinity of the magnetite powders and the presence of ferrous iron are responsible for their relatively high solubility in oxalate solutions.

The characterization of magnetic minerals and the relationship of these minerals to the magnetic susceptibility of soils that have developed on various parent materials can provide valuable information to various disciplines, such as soil evolution and environmental science. The aim of the study reported here was to investigate variations in the magnetic susceptibility (χ) of soils in western Iran due to differences in lithology and to examine the relationship of χ to ferrimagnetic minerals. Eighty samples were collected from eight parent materials taken from both intact rocks and associated soils. The soil parent materials included a range of igneous and sedimentary rocks, such as ultrabasic rocks (Eocene), basalt (Eocene), andesite (Eocene), limestone (Permian), shale (Cretaceous), marl (Cretaceous), and the Qom formation (partially consolidated fine evaporative materials, early Miocene). The 80 samples were analyzed for χ using a dual-frequency magnetic sensor and for mineralogy using X-ray diffraction (XRD). The highest χ values were found in the ultrabasic rocks and associated soils, while the lowest χ values were observed in the limestone rocks and associated soils. The pedogenic processes significantly enhanced the χ values of soils developed on the sedimentary rocks due to the formation of ferrimagnetic minerals. In contrast, χ values decreased as a result of pedogenic processes in soils developed on igneous rocks due to the dilution effects of diamagnetic materials, such as halite, calcite, phyllosilicates, and organic matter. The significant positive correlation between the XRD peak intensity of the maghemite/magnetite particles and χ values confirmed that χ values in soils are largely controlled by the distribution and content of ferrimagnetic minerals. These results show that χ measurements can be used to quantify low concentrations of ferrimagnetic minerals in the soils of semiarid regions.

Soil formation usually results in an increase in magnetic susceptibility. The magnetic properties of the products of transformation of ferrihydrite, a typical precursor of other soil Fe oxides, were examined in the present work. Synthetic 2-line ferrihydrite was aged at two temperatures (25 and 50°C) and two different relative humidities (80 and 100%) in the presence of silicate, phosphate, citrate, and tartrate as adsorbed ligands (molar anion/Fe ratio = 1–3%). The ligands delayed or prevented the transformation of ferrihydrite to hematite. The magnetic susceptibility of the ferrihydrite transformation products increased with aging, the rate of increase depending on the type of ligand added and its concentration. The largest increase in magnetic susceptibility, sixfold, was obtained with ferrihydrite in a citrate/Fe ratio of 1%, after 1500 days. The resulting magnetic products exihibited superparamagnetic behavior at room temperature and high coercivity at 5 K. The formation of an intermediate ferrimagnetic phase in the ferrihydrite-to-hematite transformation might explain the magnetic enhancement observed in many aerobic soils lacking other sources of magnetic minerals.

Evidence for the formation of maghemite from goethite due to a bushfire on acid sulfate soil at East Trinity, Australia, is presented. Oxidation of pyrite-bearing acid sulfate soils led to precipitation of goethite-impregnated leaf litter. During a major bushfire, goethite with a crystal size calculated from broadening of the 110 reflection of ∼9 nm was converted to microcrystalline maghemite (size 12 nm, 220 reflection) and hematite (17 nm, 104 reflection) in a matrix of partly combusted plant litter. Replication of this natural formation of maghemite from goethite was achieved in the laboratory by burning goethite-impregnated leaf litter.

Evidence for fire affecting the solubility of metals in Fe oxide-rich Oxisols of the Koniambo Massif of New Caledonia is presented. Acid-dissolution studies showed that Ni, Al and Cr are substituted for Fe in the structure of the Fe oxides. Thermal dehydroxylation of goethite under oxidizing conditions led to the formation of hematite and to the migration of some of these metals towards the surface of hematite crystals as indicated by their enhanced release during the early stage of dissolution. Dehydroxylation of goethite under reducing conditions led to the formation of hematite and maghemite. Nickel and Al were released preferentially during the early stages of dissolution whereas Cr was not released preferentially and may be uniformly incorporated within maghemite and hematite crystals. These results have significance to the mineral-processing industry, to geochemical exploration and to the availability of these metals to plants growing on burnt soils.

Many soils in southern Switzerland have a black color, contain a large amount of soil organic matter (SOM) and seem to have some andic properties although they did not develop on volcanic parent material. We investigated three typical ‘black’ soils to determine the mechanisms of (clay) mineral formation and transformation. We measured total element pools as well as the dithionite-, pyrophosphate-and oxalate-extractable fractions (Fe, Al, Si). The clay fraction (<2 µm) was analyzed using X-ray diffraction and FTIR spectroscopy. Iron speciation in the solid phase was determined by Mössbauer spectroscopy. With increasing weathering conditions, the plagioclase (albite) content decreases, trioctahedral species in the clay fraction such as biotite, chlorite or trioctahedral vermiculite either decompose or transform into a dioctahedral mineral such as dioctahedral vermiculite or hydroxy interlayered smectite (HIS). Typical weathering products were hydroxy interlayered vermiculite (HIV), HIS, interstratified minerals and kaolinite. The oxidation of Fe(II) into Fe(III) was evident and contributes to the transformation of trioctahedral mineral species into dioctahedral ones. In one soil, a large part of the Fe (up to 41%) was found in the form of Fe oxides. In the surface horizon, the poorly crystalline mineral ferrihydrite was dominant, while in the subsoil goethite prevailed. Maghemite (or maghemite/hematite mixture) was, furthermore, found in distinct concentrations down to a depth of ∼50 cm. The formation of this mineral requires high temperatures which means that a forest fire can influence soil mineralogy down to a considerable depth. The specific climatic conditions with periods of strong humidity alternating with periods of winter droughts, sporadic fire events and the relatively large content of poorly crystalline fractions of Fe and Al contributed to the stabilization of SOM.