Clay minerals are ubiquitous constituents in soils on Earth, are occasionally found in meteorites, and may also occur on planetary surfaces in the presence of water. However, little is known about the fundamental Mössbauer parameters (the intrinsic isomer shift, δI, the characteristic Mössbauer temperature, θM, and the recoil-free fraction, f) that are characteristic of clay minerals and critical to the correct interpretation of the Fe3+/ΣFe ratios as well as the mineral modes. Spectra of well characterized single mineral samples at multiple temperatures may be used for the determinations of f. Hence, measurements of five-layer silicates with a range of layer types are presented here: nontronite, Fe-smectite, glauconite, annite and biotite. The spectra were fitted using three different software packages: WMOSS from Science, Engineering & Education Co. in Minnesota; Recoil, from the University of Ottawa in Canada; and two programs used at the University of Ghent in Belgium. Four different approaches to modelling line shapes were used: (1) Lorentzian; (2) pseudo-Voigt (convolution of Lorentzian and Gaussian curves); (3) quadrupole-splitting distributions (QSD); and (4) a technique that does not assume a particular line shape (subsequently referred to as ‘model-independent’). Values of δI, θM and f were determined using the method of De Grave & Van Alboom (1991).

Results show that multiple doublets are routinely required by all models to represent Fe-site occupancy, even when all the Fe atoms of the same valence are in the same site, as is the case for dioctahedral smectite, nontronite, mica and glauconite. Consistent values of centre shift (δ) and quadrupole splitting (Δ) were obtained for the two distributions of M2Fe3+ in the smectites. In glauconite, a single Fe2+ doublet was clearly resolved and gave systematic values for δ, Δ and area, but the two Fe3+ doublets were less defined. In annite, two Fe2+ and two Fe3+ doublets were modelled, while three Fe2+ and one Fe3+ doublet were used for biotite. Three different programs that use Lorentzian line shapes gave very similar results for δ, Δ and area. The two different implementations of QSD line shapes gave similar but sometimes slightly different results, and the pseudo-Voigt and model-independent fits usually fell between the ranges for Lorentzian and QSD results.

The value of δI is ~0.58 mm/s for Fe3+ and ~1.31 mm/s for Fe2+ across all models and line shapes, which is expected because the Fe3+ has an additional shielding 3d electron. Values for θM data are nearly identical for Fe3+ in nontronite and Fe-smectite (~450 K), somewhat varied for Fe3+ in glauconite and biotite (θM = ~730 K and ~615 K, respectively), and relatively distinct for Fe2+ (~350 K). Some values for θM and f could not be determined due to the non-monotonic behaviour of the fitted values for δ as a function of temperature. Values of f295 were 0.821–0.917 for Fe3+ and 0.662–0.743 for Fe2+, consistent with previous studies of the recoil-free fraction in micas and other silicates. Calculated scatter in δ, Δ, area and f values as a function of different line shapes and computer software was significantly reduced at lower temperatures. Sources of error in each of the calculated parameters are discussed.

Coordinated visible/near-infrared reflectance/mid-infrared reflectance and emissivity spectra of four groups of phyllosilicates were undertaken to provide insights into the differences within and among groups of smectites, kaolinite-serpentines, chlorites and micas. Identification and characterization of phyllosilicates via remote sensing on Earth and Mars can be achieved using the OH combination bands in the 2.2–2.5 μm region and the tetrahedral SiO4 vibrations from ~8.8–12 μm (~1140–830 cm–1) and ~20–25 μm (500–400 cm–1). The sharp and well resolved OH combination bands in the 2.2–2.5 μm region provide unique fingerprints for specific minerals. Al-rich phyllosilicates exhibit OH combination bands near 2.2 μm, while these bands are observed near 2.29–2.31, 2.33–2.34 μm and near 2.35–2.37 μm for Fe3+-rich, Mg-rich and Fe2+-rich phyllosilicates, respectively. When a tetrahedral substitution of Al or Fe3+ for Si occurs, the position of the Si(Al,Fe)O4 stretching mode absorption shifts. Depending on the size of the cation, the Si(Al,Fe)O4 bending mode near 500 cm–1 is split into multiple bands that may be distinguished via hyperspectral remote sensing techniques. The tetrahedral SiO4 vibrations are also influenced by the octahedral cations, such that Al-rich, Fe-rich and Mg-rich phyllosilicates can be discriminated in reflectance and emissivity spectra based on diagnostic positions of the stretching and bending bands. Differences among formation conditions for these four groups of phyllosilicates are also discussed. Hyperspectral remote sensing can be used to identify specific phyllosilicates using electronic and vibrational features and thus provide constraints on the chemistry and formation conditions of soils.

Physical alteration of magnetite-bearing antigorite grains is investigated in this study using Mössbauer, visible/near-infrared (VNIR) and mid-IR spectroscopy coupled with scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) analyses. An expected decrease in grain size with grinding is observed using SEM. The HRTEM images illustrate that the nanophase-sized grains which adhere to larger grains have 7 Å antigorite patterns. Mössbauer spectroscopy shows the presence of antigorite, magnetite and an amorphous phase. Visible/near infrared spectra exhibit features common in serpentine. These spectra also show an increasing continuum slope with grinding, an effect which is characteristic of thin coatings or tiny grains on surfaces. Mid-IR spectra indicate the formation of fine-grained Si-OH and carbonate in these samples with grinding.

A profile within the Upper Freshwater Molasse (OSM) of eastern Switzerland was sampled. Particle-size analyses, bulk chemical analyses, cation exchange capacities and Fe fractions (oxalate- and dithionite-citrate-bicarbonate-soluble Fe, total Fe) were measured. The mineralogical composition was determined by X-ray diffraction and quantified with Rietveld analysis. The layer charge of selected fine-clay samples was determined with the alkylammonium method using chain nc = 12. The profile could be divided into a lower sequence (I) and an upper sequence (II) by a hiatus. Chemical data, particle-size distributions and calcite contents indicated that soil formation was essentially restricted to wetting-drying cycles associated with redox cycles evident from Feo/Fed and Fed/Fet ratios. A significant correlation between the d060 values of the dioctahedral smectite-illite mixed-layer phases and Feo/Fed was interpreted as the influence of microbial Fe3+ reduction, which affected both the Fe oxides and Fe-rich clay minerals. This is the first evidence that the Fe dynamics of both mineral groups may be linked. The amount of illitization also correlated with Feo/Fed, but only in the upper part of the profile. This indicates that wetting-drying cycles were necessary for the illitization process.

57Fe Mössbauer spectra of the Na+- and Ca2+-saturated forms of four ferruginous smectites,displaying a range of compositions, have been fitted with Voigtian profiles to represent (principally) two correlated distributions of isomer shifts and quadrupole splittings for the Fe3+ sites. Correlating the areas and hyperfine parameters of these distributions with simulations of the octahedral array of cations based on chemical analyses and infrared spectroscopy has enabled identification of the Fe3+ ions that contribute to the outer quadrupole doublet. The octahedral Fe3+ sites are characterized as having at least one Mg2+ nearest-cation neighbour and probably a cisconfiguration with respect to the OH– ions.

The effects of cobalt ions on the precipitation of goethite in highly alkaline media were monitored using X-ray diffraction (XRD), Mössbauer, Fourier transform infrared (FTIR) and energy dispersive X-ray (EDS) spectroscopies and field emission scanning electron microscopy (FESEM) techniques. Tetramethylammonium hydroxide was used as a precipitating agent. The precipitates were collected after heating of the precipitation systems at 160ºC for 2 h. The XRD results showed the formation of goethite structure as a single phase up to r = 6.98 (where r = 100·[Co]/([Co]+[Fe])). Cobalt ferrite was found as an additional phase in the precipitates obtained at r = 9.09 and 13.04. Mössbauer spectroscopy showed the formation of solid solutions of α-(Fe,Co)OOH. The incorporation of cobalt ions into the goethite crystal structure was monitored by a decrease in the average hyperfine magnetic field (⟨Bhf⟩). The value ⟨Bhf⟩ decreased linearly up to r = 5.66, whereas a nonlinear dependence was obtained at r = 6.98 to 13.04. Infrared (IR) bands corresponding to the bending vibrations δOH and γOH were shifted from 892 to 903 cm–1 and from 797 to 800 cm–1, respectively, up to r = 6.98. Fourier transform infrared spectroscopy lacked the sensitivity to monitor the effects of cobalt ions, demonstrated by the Mössbauer analysis. Cobalt incorporation into the crystal structure of goethite induced a gradual elongation of α-(Fe,Co)OOH particles along the crystallographic c axis. The formation of α-(Fe,Co)OOH nanowires was shown at r ⩾6.98. These nanowires were ~700 nm long, whereas their diameter was ~15–20 nm. The majority of the cobalt ferrite particles were in the nanosize range, as observed by FE-SEM. On the basis of the Co/Fe ratio measured by EDS, it appears that the cobalt ferrite particles were not fully stoichiometric.

The clay-mineral fraction of samples from a bentonite deposit in the Zvolenská kotlina Basin (Slovakia), formed by the alteration of andesitic pyroclastics, was dominated by Fe-bearing montmorillonite of relatively low charge. The total Fe content of the samples ranged from 3.58 to 5.81 wt.% Fe. Variable-temperature Mössbauer spectroscopy revealed that structural Fe(III) in smectite accounts for 70–90% of the total Fe in the unfractionated samples. No structural Fe(II) was observed by Mössbauer spectroscopy, but a small amount was detected by wet chemical analysis. The remainder of the Fe is present in oxide and/or oxyhydroxide phases dominated by poorly ordered goethite and hematite. The hyperfine parameters of the Mössbauer spectra for the raw bentonite are consistent with structural Fe(III) in an aluminosilicate phase mixed with varying quantities of hematite, goethite and possibly maghemite. Except in the fine fraction of sample L28, the hematite failed to undergo the Morin transition, as shown by the negative values for quadrupole splitting at 298 K and 6 K.

Weathered soil material derived from tectonically emplaced serpentinized ultrabasic intrusive rocks of southern Cameroon has received considerable attention from mining companies due to its extractable-metal (i.e. Ni, Co) potential. As these cations can be incorporated into Fe oxides, it was deemed appropriate to study the mineralogical assemblage of a highly weathered serpentinite soil profile from the area. This study focuses on the different Fe-oxide phases, which were investigated using 57Fe Mössbauer spectroscopy, showing goethite and hematite as the dominant Fe oxides throughout the weathering profile. These minerals, in association with gibbsite and kaolinite, indicate an advanced degree of weathering. The clay fraction of the ‘Lower Limonite’ layer, above the saprolite and at a depth of 7 m, is very rich in goethite, whereas hematite and magnetite are almost absent. Above this layer, the hematite content in the fine-earth and clay fractions increases upwards, while the goethite content remains constant. The significant substitution and change in the particle size of the goethite and the poor crystallinity of hematite, as indicated by the hyperfine parameters and XRD, suggest that the upper material evolved under different pedological conditions compared to the deeper layers. The mixed composition of the upper layers (above 7 m), which contain muscovite and a relatively chaotic distribution of trace elements, suggests ancient mica-schist capping and possibly different cycles of erosion and pedimentation.

Over the past several decades, kaolin has been used intensively in the paper industry as a coating and filler material. These applications require kaolin of a high brightness grade, which depends heavily on the level of impurities (mainly Fe-bearing minerals such as Fe oxides and hydroxides) and may be improved by beneficiation processes involving grain-size classification, magnetic separation and chemical treatments. This investigation was carried out on five Brazilian kaolin samples of different geographical and geological origins. Granulometric, mineralogical, chemical and physical characterizations were performed on all samples before and after the beneficiation process.

Chemical compositions were determined by X-ray fluorescence and the most important crystalline phases were identified using X-ray diffraction. Kaolinite is the dominant mineralogical phase with minor amounts of muscovite and quartz. The nature of Fe impurities was investigated by electron spin resonance and 57Fe Mössbauer spectroscopy. For all studied kaolin samples, Fe ions (Fe3+ and Fe2+) are present in variable amounts, in the kaolinite structure and also in Fe oxides (magnetite, hematite and goethite). The beneficiation procedure aims to remove these Fe oxides and was found to be most efficient for the Mogi das Cruzes kaolin. The Seridó kaolin had the best whiteness index observed among the analysed samples.

This review focuses on the clay mineralogy of the most important Brazilian soils: the Latosols, which cover >60% of the country by area, and occur in association with other soils. They are typically deep, highly-weathered soils, dominated by low-activity 1:1 clay minerals and Fe and Al oxyhydroxides, with varying proportions of these minerals, depending on parent material and weathering intensity. They are usually of low fertility, although eutric types also occur. Latosols are generally correlated with Oxisols (American soil taxonomy) and Ferralsols (WRB system). Clay mineralogy is typically monotonous: kaolinite, gibbsite, hematite, goethite, maghemite and Ti minerals (mainly ilmenite and anatase) are the prominent mineral phases in the clay fraction. Some Latosols developing on basalt from southern Brazil contain significant amounts of hydroxyl-interlayed vermiculite. Among the pedogenic oxides the most frequent are goethite (α-FeOOH), indicated by yellowish colours (2.5Y–10YR; in the absence of hematite), and hematite (α-Fe2O3), which imbues reddish colors (2.5YR–5R), even when present in very minor amounts. Maghemite (γ-Fe2O3) is less frequent; it imparts a reddish-brown colour (5YR–2.5YR) and magnetic properties. Both goethite and hematite show Al-substitution, with a greater relative proportion in soil goethites. Hence, in similar drainage conditions, goethite is less prone to dissolution than hematite. Most reddish Latosols also contain maghemite, due to partial or complete oxidation of magnetite, which generally occurs naturally or is fire-induced. Magnetite and/or maghemite are associated with trace elements which are important in plant nutrition, such as Cu, Zn and Co. The contents of gibbsite in Latosols are extremely variable, from a complete absence in brown Latosols, to 54% in red Latosols from mafic rocks. Relatively large amounts of gibbsite are found in the clay fraction of these soils and this mineral is important in P sorption in deeply weathered Latosols in association with goethite and hematite. Even though most Latosols are dystrophic, some are eutrophic, revealing an unusually large base saturation in areas under ustic regimes where the parent material is particularly rich in bases, such as basalts. This eutrophic nature is attributed to the protecting role of micro-aggregates in ferric red Latosols, which retard baseleaching from the inner aggregate. At the other extreme, some Brazilian Latosols are acric and positively-charged in sub-surface horizons, as revealed by the relationship pH KCl > pH H2O. These acric Latosols are the result of long-term weathering and intensive leaching, during which pH tends to increase to values close to the zero point charge of Fe and Al oxides (between 6 and 7), greatly increasing P adsorption, which is mainly attributed to gibbsite, goethite and hematite. Soil kaolinites in Brazilian Latosols are mostly of low crystallinity, with Hughes and Brown indexes of between 6 and 15. In this review we have discussed the role of these clay-fraction minerals in soil genesis and fertility, highlighting the marked role of inheritance from deeply-weathered parent material. Latosols typically retain large amounts of Fe oxides, some of which are magnetic, with spontaneous magnetization >1 J T–1 kg–1. In this regard, reddish Latosols developed from mafic rocks are the most representative magnetic soils, and cover as much as 3.9% of Brazil. An overview of magnetic soils on four representative examples of mafic lithologies is presented, together with some aspects of their Fe-oxide mineralogy and related field and laboratory technqiues.