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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.

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The reduction of structural Fe in smectite may be mediated either abiotically by reaction with chemical reducing agents or biotically by reaction with various bacterial species. The effects of abiotic reduction on clay surface chemistry are much better known than the effects of biotic reduction, and differences between them are still in need of investigation. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in nontronite on the clay structure as observed by variabletemperature Mössbauer spectroscopy. Biotic reduction was accomplished by incubating Na-saturated Garfield nontronite (sample API 33a) with Shewanella oneidensis strain MR-1 (Fe II /total Fe achieved was ~17 %). Partial abiotic reduction (Fe II /total Fe ~23 %) was achieved using pH-buffered sodium dithionite. The nontronite was also reduced abiotically to Fe II /total Fe ~96 %. Parallel samples were reoxidized by bubbling O 2 gas through the reduced suspensions at room temperature prior to Mössbauer analysis at 77 and 4 K. At 77 K, the reduction treatments all gave spectra composed of doublets for structural Fe II and Fe III in the nontronite. The spectra for reoxidized samples were largely restored to that of the unaltered sample, except for the sample reduced to 96 %. At 4 K, the spectrum for the 96 % reduced sample was highly complex and clearly reflected magnetic order in the sample. When partially reduced, the spectrum also exhibited magnetic order, but the features were completely different depending on whether reduced biotically or abiotically. The biotically reduced sample appeared to contain distinctly separate domains of Fe II and Fe III within the structure, whereas partial abiotic reduction produced a spectrum representative of Fe II -Fe III pairs as the dominant domain type. The 4 K spectra of the partially reduced, fully reoxidized samples were virtually the same as at 77 K, whereas reoxidation of the 96 % reduced sample produced a spectrum consisting of a magnetically ordered sextet with a minor contribution from a Fe II doublet, indicating significant structural alterations compared to the unaltered sample.

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