XPS study of the major minerals in bauxite: Gibbsite, bayerite and (pseudo-)boehmite

Synthetic corundum (Al2O3), gibbsite (Al(OH)(3)), bayerite (Al(OH)(3)), boehmite (AlO(OH)) and pseudoboehmite (AlO(OH)) have been studied by high resolution XPS. The chemical compositions based on the XPS survey scans were in good agreement with the expected composition. High resolution A12p scans showed no significant changes in binding energy, with all values between 73.9 and 74.4 eV. Only bayerite showed two transitions, associated with the presence of amorphous material in the sample. More information about the chemical and crystallographic environment was obtained from the 0 Is high resolution spectra. Here a clear distinction could be made between oxygen in the crystal structure, hydroxyl groups and adsorbed water. Oxygen in the crystal structure was characterised by a binding energy of about 530.6 eV in all minerals. Hydroxyl groups, present either in the crystal structure or on the surface, exhibited binding energies around 531.9 eV, while water on the surface showed binding energies around 533.0 eV. A distinction could be made between boehmite and pseudoboehmite based on the slightly lower ratio of oxygen to hydroxyl groups and water in pseudoboehmite. (c) 2005 Elsevier Inc. All rights reserved.

Étude des phénomènes d'entartrage de la gibbsite sur les surfaces métalliques

Le procédé Bayer est cyclique et il permet d'extraire les hydrates d'alumine, contenu dans le minerai de bauxite. L'alumine est la matière première nécessaire pour la production de l'aluminium métallique par le procédé d'électrolyse. La solubilisation des hydrates d'alumine est effectuée dans une solution d'hydroxyde de sodium concentrée, liqueur Bayer, à haute température et pression. Il existe deux types de procédé : un procédé dit à basse température (150ÀC) et un procédé dit haute température (250ÀC). Selon la température utilisée, certaines impuretés présentes dans la bauxite vont être solubilisées comme par exemple la silice, le fer ou le titane. Comme le procédé est basé sur la solubilisation puis sur la précipitation des hydrates d'alumine, la solution est chauffée puis refroidie par une série d'échangeurs de chaleur. Ces changements de température impliquent des variations dans les conditions de saturation et sursaturation ce qui va conséquemment causer la formation de tartre dans le procédé. Selon la température du procédé utilisé, la composition chimique du tartre formé peut être différente. Dans le but d'inhiber partiellement ou totalement la cristallisation de la gibbsite, ou hydrate d'alumine, sur les surfaces métalliques, la compréhension des paramètres influençant sa formation est nécessaire. L'un des moyens de réduire ou d'inhiber la formation du tartre est de modifier les énergies de surface entre les surfaces métalliques et la solution de liqueur Bayer. Pour ce faire, des métaux ayant des propriétés différentes seront étudiés en entartrage et des composés organiques seront ajoutées à la solution d'hydroxyde de sodium afin de modifier l'interface entre ces métaux et la solution. L'influence des hydrates d'alumine et des différents composés organiques sur les métaux sera déterminer [i.e. déterminée] par des mesures d'isothermes d'adsorption, de potentiels zêta et d'angles de contact, dans le but d'établir une corrélation entre l'interface métal/solution et les temps de nucléation mesurés en entartrage. Un deuxième volet consiste en la fabrication d'un montage en laboratoire permettant d'effectuer la formation reproductible du tartre de freudenbergite. La freudenbergite est un tartre à base de titane qui se forme dans le procédé à haute température. Cette étude démontre que la formation du tartre dans le procédé Bayer est un phénomène de formation de cristaux de gibbsite en solution qui vont adhérer aux défauts de surfaces des surfaces métalliques. En ce sens, la rugosité de surface des métaux est le facteur déterminant pour la formation du tartre dans le procédé Bayer. Des tests d'entartrage réalisés au laboratoire sur cinq métaux différents démontrent une corrélation évidente entre la rugosité de surface, mesurée par microscope à force atomique, et les temps de nucléation obtenus en entartrage. Les mesures d'interactions interfaciales des aluminates de sodium sur les métaux étudiés, en présence ou non de composés organiques, ne permettent pas d'établir de corrélation avec les temps de nucléation obtenus en entartrage. Par contre, l'allongement de l'entartrage en présence de gluconate et de tartrate de sodium, des composés inhibiteurs de croissance des cristaux de gibbsite, confirme le phénomène de formation du tartre par des cristaux formés en solution. La croissance des cristaux de tartre étant partiellement inhibée, les temps de nucléation vont être allongés lors des tests d'entartrage. À l'inverse, l'EDTA favorise la formation de plusieurs cristaux en solution, ce qui diminue significativement la vitesse d'entartrage lorsqu'elle est ajoutée dans la liqueur Bayer. Afin de confirmer que la rugosité de surface est le facteur prédominant dans la formation du tartre dans le procédé Bayer, dans nos conditions de laboratoire, des tests d'entartrage sont effectués sur une surface d'or recouverte d'une monocouche d'alcane thiols. Ces tests démontrent que le changement de nature de la surface d'or ne permet pas de changer significativement le temps de nucléation de l'or dans nos conditions d'entartrage. Un montage expérimental comportant un four et quatre autoclaves, contrôlé par un système informatique a permis d'effectuer la formation de tartre de freudenbergite de façon reproductible au laboratoire.

Mineralogical characterization of a highly-weathered soil by the Rietveld Method

The mineralogical characterization through mineral quantification of Brazilian soils by X-ray diffraction data using the Rietveld Method is not common. A mineralogical quantification of an Acric Ferralsol from the Ponta Grossa region, state of Paraná, Brazil, was carried out using this Method with X-Ray Diffraction data to verify if this method was suitable for mineral quantification of a highly-weathered soil. The A, AB and B3 horizons were fractioned to separate the different particle sizes: clay, silt, fine sand (by Stokes Law) and coarse sand fractions (by sieving), with the procedure free of chemical treatments. X-ray Fluorescence, Inductively Coupled Plasma Atomic Emission Spectrometry, Infrared Spectroscopy and Mössbauer Spectroscopy were used in order to assist the mineral identification and quantification. The Rietveld Method enabled the quantification of the present minerals. In a general way, the quantitative mineralogical characterization by the Rietveld Method revealed that quartz, gibbsite, rutile, hematite, goethite, kaolinite and halloysite were present in the clay and silt fractions of all horizons. The silt fractions of the deeper horizons were different from the more superficial ones due to the presence of large amounts of quartz. The fine and the coarse sand fractions are constituted mainly by quartz. Therefore, a mineralogical quantification of the finer fraction (clay and silt) by the Rietveld Method was successful.

Mineralogia de um latossolo vermelho distrófico submetido a diferentes manejos por 24 anos

Atualmente, procuram-se sistemas de manejo que preservem ou melhorem as qualidades do solo, tanto mineralógicas como orgânicas, priorizando maior produtividade. Este trabalho teve como objetivo verificar qualitativamente, por meio das técnicas de fluorescência de raios X, difração de raios X e infravermelho com transformada de Fourier, os efeitos provocados pela utilização dos manejos: plantio convencional, preparo mínimo e plantio direto, por 24 anos, na mineralogia de um Latossolo Vermelho distrófico de Ponta Grossa, PR. Não foram observadas mudanças significativas na mineralogia do Latossolo estudado, por meio das técnicas utilizadas, quanto aos diferentes manejos durante os anos de sua aplicação. Pôde-se verificar, qualitativamente, a presença dos minerais gibbsita, caulinita, haloisita, montmorilonita, hematita, rutilo, anatásio, goethita e quartzo.

Deep weathering and landscape evolution in a tropical plateau

The thick weathering profiles of humid tropical areas are an important, yet generally neglected, source of information on landscape evolution. Six complete profiles of the weathering mantle were sampled by drilling on the three stepped levels of the Campos do Jordao Plateau, on the NW flank of the Continental Rift of Southeastern Brazil. Mineralogical and micromorphological analyses of drill core samples, complemented by geochemical interpretations and by previous data on the upper saprolite, indicate continuity of a general lateritic trend during the entire process of mantle formation. Lateritization phases of different intensity were defined and considered to reflect adjustment to changes in environmental conditions created by the gradual uplift of the plateau to its present position. Older and more superficial materials related to intense lateritic weathering are characterized by allitization with direct formation of gibbsite from silicates, probably related to tropical climates existing immediately before the formation of the continental rift, during the Paleogene, and also before any significant increase in altitude. Monosialitization phase with general kaolinitization and restricted indirect formation of gibbsite from silicates could be associated to less aggressive climates that followed the Neogene (Miocene?) accentuation of uplift rates along the continental rift. The changes produced by uplift in the tropical climate eventually favored the development of a podzolization trend in soils above 1800m. (C) 2011 Elsevier BM. All rights reserved.

Study of soils by thermal analysis

The study of soils is very important in the geological and geological engineering researches. A study of ten samples of soils was carried out by thermal analysis, and X-Ray Fluorescence Spectrometry to understand soil evolution in Angra dos Reis region, Rio de Janeiro State, Brazil. The sample collection sites were chosen based on geological characteristics, the soil layer thickness, the soil composition pattern, and whether or not it was moved either by erosion or by gravitational shifts. Because of the humid tropical climatic condition, natural soils tend to show great thickness of weathered mantles with formation of saprolites and saprolite soils. Kaolinite is an important secondary mineral which can be formed from many different minerals, like k-mica and k-feldspar and can be weathered to gibbsite. The results from TG/DTG and DTA indicated which soils had more weathering, and the same results were obtained by XRF, when silica/aluminum ratios from samples are compared with thermal analysis results.

Separation of silica from bauxite via froth flotation

This paper reports an innovative development: concentrating gibbsite via reverse froth flotation in order to obtain a metallurgical-grade bauxite concentrate. Tailings from an industrial plant have undergone attrition scrubbing and desliming; the quartz silica contained in the tailings has undergone flotation. Starch was used as a depressant, and ether-amine as the cationic collector. Optimum pH is around 10.0. In pilot plant scale, a metallurgical-grade concentrate was obtained by assaying 42.3% available alumina with an alumina/insoluble silica mass ratio of 11.1. It contained the gibbsite and the iron and titanium bearing minerals. The concentrate was further upgraded by magnetic separation, leading to 54.0% available alumina, with an alumina/insoluble silica mass ratio of 12.6 at an overall available alumina recovery of 69.3% in the final concentrate (non-magnetic product). (C) 2008 Elsevier Ltd. All rights reserved.

Podzolization as a deferralitization process: dynamics and chemistry of ground and surface waters in an Acrisol-Podzol sequence of the upper Amazon Basin

Hydrochemical processes involved in the development of hydromorphic Podzols are a major concern for the upper Amazon Basin because of the extent of the areas affected by such processes and the large amounts of organic carbon and associated metals exported to the rivers. The dynamics and chemical composition of ground and surface waters were studied along an Acrisol-Podzol sequence lying in an open depression of a plateau. Water levels were monitored along the sequence over a period of 2 years by means of piezometers. Water was sampled in zero-tension lysimeters for groundwater and for surface water in the drainage network of the depression. The pH and concentrations of organic carbon and major elements (Si, Fe and Al) were determined. The contrasted changes reported for concentrations of Si, organic carbon and metals (Fe, Al) mainly reflect the dynamics of the groundwater and the weathering conditions that prevail in the soils. Iron is released by the reductive dissolution of Fe oxides, mostly in the Bg horizons of the upslope Acrisols. It moves laterally under the control of hydraulic gradients and migrates through the iron-depleted Podzols where it is exported to the river network. Aluminium is released from the dissolution of Al-bearing minerals (gibbsite and kaolinite) at the margin of the podzolic area but is immobilized as organo-Al complexes in spodic horizons. In downslope positions, the quick recharge of the groundwater and large release of organic compounds lead to acidification and a loss of metals (mainly Al), previously stored in the Podzols.

Soil mineralogy of mangrove forests from the state of Sao Paulo, Southeastern Brazil

The minerals of the clay fraction in estuarine plains are mainly detrital being a mixture of marine and continental sediments, but can also be authigenic. Because of the importance of mangrove ecosystems in tropical estuarine areas and the relatively few existing studies of the mineralogical composition of soils in these environments, the aim of this study was to determine the mineralogical assemblage and identify potential contrasts along the coast of the State of Sao Paulo. Soils from I I mangroves distributed along the coastal plain of the State of Sao Paulo were sampled at depths of 0 to 20 and 60 to 80 cm, and samples of suspended sediments from the Ribeira do Iguape River were collected for analysis. Mineralogical analyses were performed on the clay and silt fractions by x-ray diffraction (XRD) and transmission electron microscopy, and fresh soil samples were analyzed by scanning electron microscopy-energy dispersive spectrometry and suspended sediments by XRD. The silt fraction contained quartz, feldspars, gibbsite, kaolinite, illite, and vermiculite, and the clay fraction contained smectite, kaolinite, illite, gibbsite, quartz, and feldspars. Locally, vermiculite, biotite, anatase, halloysite, and goethite may occur because of recent transport of sediments to the system. Pyrite was identified in fresh samples. The allochthonous minerals found either were terrestrial and transported by rivers or had originated from the continental platform by past transgressive events. We suggest that the neoformation of smectite and kaolinite occurs in mangrove soils. Different geomorphological settings along the Sao Paulo coast appear to regulate mineral distribution in mangrove soils.

Components of Surface Charge in Tropical Soils With Contrasting Mineralogies

Study of surface electric charges of soil colloids helps in understanding the physicochemical phenomena that influence the capacity of retaining nutrients and their availability to plants. The structural charge (sigma(0), (min)), the variable charge (sigma(q, min)), and the organic matter (OM) charge (sigma(total) (OM)) of 12 tropical soils with contrasting mineralogies were evaluated based on the difference of selectivity for Cs(+) and Li(+) between the functional ionizable surfaces groups and the mineral 2:1 siloxane surface. Soils were divided into three groups: G1, soils with a predominance of kaolinite and gibbsite in the clay fraction; G2, soils with hydroxy-interlayered 2:1 minerals; and G3, soils with smectite but without hydroxy-interlayered 2:1 minerals. The Cs absorption method was efficient for detecting the charge components in tropical soils. The mineral structural charge contributed 11% and 16%, 28% and 31%, and 52% and 59% of total soil charge of A and B horizons of soils from groups G 1, G2, and G3, respectively. On the other hand, OM contributed 53% and 37%, 48% and 41%, and 21% and 20% of total charge for the same samples, respectively, In highly weathered soils of group G I and, to a lesser extent, in soils in group G2, surface charges depended mainly on their variable components, resulting from the OM (sigma(toal) (OM)), as well as from imperfections found in 1:1 minerals (sigma(q, min)). The importance of OM in determining the magnitude of electric charges in humid tropical soils is highlighted.

Genesis and classification of Oxisols in a highland toposequence of the upper Jequitinhonha Valley (MG)

The Brazilian System of Soil Classification (SiBCS) is a taxonomic system, open and in permanent construction, as new knowledge on Brazilian soils is obtained. The objective of this study was to characterize the chemical, physical, morphological, micro-morphological and mineralogical properties of four pedons of Oxisols in a highland toposequence in the upper Jequitinhonha Valley, emphasizing aspects of their genesis, classification and landscape development. The pedons occupy the following slope positions: summit - Red Oxisol (LV), mid slope (upper third) - Yellow-Red Oxisol (LVA), lower slope (middle third)- Yellow Oxisol (LA) and bottom of the valley (lowest third) - "Gray Oxisol" ("LAC"). These pedons were described and sampled for characterization in chemical and physical routine analyses. The total Fe, Al and Mn contents were determined by sulfuric attack and the Fe, Al and Mn oxides in dithionite-citrate-bicarbonate and oxalate extraction. The mineralogy of silicate clays was identified by X ray diffraction and the Fe oxides were detected by differential X ray diffraction. Total Ti, Ga and Zr contents were determined by X ray fluorescence spectrometry. The "LAC" is gray-colored and contains significant fragments of structure units in the form of a dense paste, characteristic of a gleysoil, in the horizons A and BA. All pedons are very clayey, dystrophic and have low contents of available P and a pH of around 5. The soil color was related to the Fe oxide content, which decreased along the slope. The decrease of crystalline and low- crystalline Fe along the slope confirmed the loss of Fe from the "LAC". Total Si increased along the slope and total Al remained constant. The clay fraction in all pedons was dominated by kaolinite and gibbsite. Hematite and goethite were identified in LV, low-intensity hematite and goethite in LVA, goethite in LA. In the "LAC", no hematite peaks and goethite were detected by differential X ray diffraction. The micro-morphology indicated prevalence of granular microstructure and porosity with complex stacking patterns.. The soil properties in the toposequence converged to a single soil class, the Oxisols, derived from the same source material. The landscape evolution and genesis of Oxisols of the highlands in the upper Jequitinhonha Valley are related to the evolution of the drainage system and the activity of excavating fauna.

Relationship between soil oxidizable carbon and physical, chemical and mineralogical properties of umbric ferralsols

The occurrence of Umbric Ferralsols with thick umbric epipedons (> 100 cm thickness) in humid Tropical and Subtropical areas is a paradox since the processes of organic matter decomposition in these environments are very efficient. Nevertheless, this soil type has been reported in areas in the Southeast and South of Brazil, and at some places in the Northeast. Aspects of the genesis and paleoenvironmental significance of these Ferralsols still need a better understanding. The processes that made the umbric horizons so thick and dark and contributed to the preservation of organic carbon (OC) at considerable depths in these soils are of special interest. In this study, eight Ferralsols with a thick umbric horizon (UF) under different vegetation types were sampled (tropical rain forest, tropical seasonal forest and savanna woodland) and their macromorphological, physical, chemical and mineralogical properties studied to detect soil characteristics that could explain the preservation of high carbon amounts at considerable depths. The studied UF are clayey to very clayey, strongly acidic, dystrophic, and Al-saturated and charcoal fragments are often scattered in the soil matrix. Kaolinites are the main clay minerals in the A and B horizons, followed by abundant gibbsite and hydroxyl-interlayered vermiculite. The latter was only found in UFs derived from basalt rock in the South of the country. Total carbon (TC) ranged from 5 to 101 g kg-1 in the umbric epipedon. Dichromate-oxidizable organic carbon represented nearly 75 % of TC in the thick A horizons, while non-oxidizable C, which includes recalcitrant C (e.g., charcoal), contributed to the remaining 25 % of TC. Carbon contents were not related to most of the inorganic soil variables studied, except for oxalate-extractable Al, which individually explained 69 % (P < 0.001) of the variability of TC in the umbric epipedon. Clay content was not suited as predictor of TC or of the other studied C forms. Bulk density, exchangeable Al3+, Al saturation, ECEC and other parameters obtained by selective extraction were not suitable as predictors of TC and other C forms. Interactions between organic matter and poorly crystalline minerals, as indicated by oxalate-extractable Al, appear to be one of the possible organic matter protection mechanisms of these soils.

Highlands of the upper Jequitinhonha valley, Brazil: II - mineralogy, micromorphology, and landscape evolution¹

Palm swanp formations, the so-called veredas, typically occur in the Brazilian biome known as "Cerrado" (savanna-like vegetation), especially on flattened areas or tablelands (chapadas). The aim of this study was to characterize the mineralogy and micromorphology of soil materials from a representative toposequence of the watershed of the vereda Lagoa do Leandro, located in Minas Novas, state of Minas Gerais, Brazil, on plains in the region of the upper Jequitinhonha valley, emphasizing essential aspects of their genesis and landscape evolution. The toposequence is underlain by rocks of the Macaúbas group and covered with detrital and metamorphic rocks (schists of Proterozoic diamictites). The soil profiles were first pedologically described; samples of the disturbed and undisturbed soils were collected from all horizons for further micromorphological and mineralogical analyses. The mineralogical analysis was mainly based on powder X ray diffractometry (XRD) and micromorphological descriptions of thin sections under a petrographic microscope. The soils from the bottom to the top of this toposequence were classified as: Typic Albaquult (GXbd), Xanthic Haplustox, gray color, here called "Gray Haplustox" ("LAC"), Xanthic Haplustox (LA) and Typic Haplustox (LVA). The clay mineralogy of all soils was found to be dominated by kaolinite. In soil of LA and LVA, the occurrence of goethite, gibbsite, and anatase was evidenced; "LAC" also contained anatase and the GXbd, illite, anatase, and traces of vermiculite. The micromorphological analyses of the LVA, LA and "LAC" soils showed the prevalence of a microaggregate-like or granular microstructure, and aggregate porosity has a stacked/packed structure, which is typical of Oxisols. A massive structure was observed in GXbd material, with the presence of illuviation cutans of clay minerals and iron compounds. Paleogleissolos, which are strongly weathered, due to the action of the excavating fauna , and resulted in the present "LAC". The GXbd at the base of the vereda preserved the physical, mineralogical and micromorphological properties that are typical of a pedogenesis with a strong influence of long dry periods.

Mineralogy of the clay fraction of Alfisols in two slope curvatures: III - spatial variability

A good knowledge of the spatial distribution of clay minerals in the landscape facilitates the understanding of the influence of relief on the content and crystallographic attributes of soil minerals such as goethite, hematite, kaolinite and gibbsite. This study aimed at describing the relationships between the mineral properties of the clay fraction and landscape shapes by determining the mineral properties of goethite, hematite, kaolinite and gibbsite, and assessing their dependence and spatial variability, in two slope curvatures. To this end, two 100 × 100 m grids were used to establish a total of 121 regularly spaced georeferenced sampling nodes 10 m apart. Samples were collected from the layer 0.0-0.2 m and analysed for iron oxides, and kaolinite and gibbsite in the clay fraction. Minerals in the clay fraction were characterized from their X-ray diffraction (XRD) patterns, which were interpreted and used to calculate the width at half height (WHH) and mean crystallite dimension (MCD) of iron oxides, kaolinite, and gibbsite, as well as aluminium substitution and specific surface area (SSA) in hematite and goethite. Additional calculations included the goethite and hematite contents, and the goethite/(goethite+hematite) [Gt/(Gt+Hm)] and kaolinite/(kaolinite+gibbsite) [Kt/(Kt+Gb)] ratios. Mineral properties were established by statistical analysis of the XRD data, and spatial dependence was assessed geostatistically. Mineralogical properties differed significantly between the convex area and concave area. The geostatistical analysis showed a greater number of mineralogical properties with spatial dependence and a higher range in the convex than in the concave area.

Mineralogy of the clay fraction of alfisols in two slope curvatures: IV - spatial correlation with physical properties

Although the influence of clay mineralogy on soil physical properties has been widely studied, spatial relationships between these features in Alfisols have rarely been examined. The purpose of this work was to relate the clay minerals and physical properties of an Alfisol of sandstone origin in two slope curvatures. The crystallographic properties such as mean crystallite size (MCS) and width at half height (WHH) of hematite, goethite, kaolinite and gibbsite; contents of hematite and goethite; aluminium substitution (AS) and specific surface area (SSA) of hematite and goethite; the goethite/(goethite+hematite) and kaolinite/(kaolinite+gibbsite) ratios; and the citrate/bicarbonate/dithionite extractable Fe (Fe d) were correlated with the soil physical properties through Pearson correlation coefficients and cross-semivariograms. The correlations found between aluminium substitution in goethite and the soil physical properties suggest that the degree of crystallinity of this mineral influences soil properties used as soil quality indicators. Thus, goethite with a high aluminium substitution resulted in large aggregate sizes and a high porosity, and also in a low bulk density and soil penetration resistance. The presence of highly crystalline gibbsite resulted in a high density and micropore content, as well as in smaller aggregates. Interpretation of the cross-semivariogram and classification of landscape compartments in terms of the spatial dependence pattern for the relief-dependent physical and mineralogical properties of the soil proved an effective supplementary method for assessing Pearson correlations between the soil physical and mineralogical properties.