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.

Water–rock interactions : an investigation of the relationships between mineralogy and groundwater composition and flow in a subtropical basalt aquifer

A holistic study of the composition of the basalt groundwaters of the Atherton Tablelands region in Queensland, Australia was undertaken to elucidate possible mechanisms for the evolution of these very low salinity, silica- and bicarbonate-rich groundwaters. It is proposed that aluminosilicate mineral weathering is the major contributing process to the overall composition of the basalt groundwaters. The groundwaters approach equilibrium with respect to the primary minerals with increasing pH and are mostly in equilibrium with the major secondary minerals (kaolinite and smectite), and other secondary phases such as goethite, hematite, and gibbsite, which are common accessory minerals in the Atherton basalts. The mineralogy of the basalt rocks, which has been examined using X-ray diffraction and whole rock geochemistry methods, supports the proposed model for the hydrogeochemical evolution of these groundwaters: precipitation + CO 2 (atmospheric + soil) + pyroxene + feldspars + olivine yields H 4SiO 4, HCO 3 -, Mg 2+, Na +, Ca 2+ + kaolinite and smectite clays + amorphous or crystalline silica + accessory minerals (hematite, goethite, gibbsite, carbonates, zeolites, and pyrite). The variations in the mineralogical content of these basalts also provide insights into the controls on groundwater storage and movement in this aquifer system. The fresh and weathered vesicular basalts are considered to be important in terms of zones of groundwater occurrence, while the fractures in the massive basalt are important pathways for groundwater movement.

Iron nodules in ferric soils of the Fraser Coast, Australia : relicts of laterisation or features of contemporary weathering and pedogenesis?

The genesis of ferruginous nodules and pisoliths in soils and weathering profiles of coastal southern and eastern Australia has long been debated. It is not clear whether iron (Fe) nodules are redox accumulations, residues of Miocene laterite duricrust, or the products of contemporary weathering of Fe-rich sedimentary rocks. This study combines a catchment-wide survey of Fe nodule distribution in Poona Creek catchment (Fraser Coast, Queensland) with detailed investigations of a representative ferric soil profile to show that Fe nodules are derived from Fe-rich sandstones. Where these crop out, they are broken down, transported downslope by colluvial processes, and redeposited. Chemical and physical weathering transforms these eroded rock fragments into non-magnetic Fe nodules. Major features of this transformation include lower hematite/goethite and kaolinite/gibbsite ratios, increased porosity, etching of quartz grains, and development of rounded morphology and a smooth outer cortex. Iron nodules are commonly concentrated in ferric horizons. We show that these horizons form as the result of differential biological mixing of the soil. Bioturbation gradually buries nodules and rock fragments deposited at the surface of the soil, resulting in a largely nodule-free 'biomantle' over a ferric 'stone line'. Maghemite-rich magnetic nodules are a prominent feature of the upper half of the profile. These are most likely formed by the thermal alteration of non-magnetic nodules located at the top of the profile during severe bushfires. They are subsequently redistributed through the soil profile by bioturbation. Iron nodules occurring in the study area are products of contemporary weathering of Fe-rich rock units. They are not laterite duricrust residues nor are they redox accumulations, although redox-controlled dissolution/re-precipitation is an important component of post-depositional modification of these Fe nodules.

An investigation of goethite-seeded Al(OH)3 precipitation using in situ X-ray diffraction and Rietveld-based quantitative phase analysis

An in situ X-ray diffraction investigation of goethite-seeded Al(OH)3 precipitation from synthetic Bayer liquor at 343 K has been performed. The presence of iron oxides and oxyhydroxides in the Bayer process has implications for alumina reversion, which causes significant process losses through unwanted gibbsite precipitation, and is also relevant for the nucleation and growth of scale on mild steel process equipment. The gibbsite, bayerite and nordstrandite polymorphs of Al(OH)3 precipitated from the liquor; gibbsite appeared to precipitate first, with subsequent formation of bayerite and nordstrandite. A Rietveld-based approach to quantitative phase analysis was implemented for the determination of absolute phase abundances as a function of time, from which kinetic information for the formation of the Al(OH)3 phases was determined.

The roles of adsorption in hydrate precipitation

It has been well established that organic compounds with adjacent hydroxyl groups in Bayer process liquor can inhibit gibbsite precipitation by acting as seed poisons. The degree of inhibition is a function of the number and stereochemistry of the hydroxyl groups. Seed poisons generally adsorb strongly onto hydrate surfaces, implying that surface coverage is the mechanism for yield inhibition. There are examples however of organics that strongly adsorb but do not lead to yield inhibition. There is a possibility that this apparent contradiction may be an artifact of differences in conditions between the adsorption and precipitation experiments. The present work investigates the adsorption and inhibition effects of a range of compounds under strictly similar conditions to clarify the role of adsorption on yield inhibition.

Controls on intense silicate weathering in a tropical river, southwestern India

The Silicate Weathering Rate (SWR) and associated Carbon dioxide Consumption Rate (CCR) in tropical silicate terrain is assessed through a study of the major ion chemistry in a small west flowing river of Peninsular India, the Nethravati River. The specific features of the river basin are high mean annual rainfall and temperature, high runoff and a Precambrian basement composed of granitic-gneiss, charnockite and minor metasediments. The water samples (n = 56) were collected from three locations along the Nethravati River and from two of its tributaries over a period of twelve months. Chemical Weathering Rate (CWR) for the entire watershed is calculated by applying rainwater correction using river chloride as a tracer. Chemical Weathering Rate in the Nethravati watershed is estimated to 44 t.km(-2).y(-1) encompassing a SWR of 42 t.km(-2).y(-1) and a maximum carbonate contribution of 2 t.km(-2).y(-1). This SWR is among the highest reported for granito-gneissic terrains. The assessed CCR is 2.9 . 10(5) mol.km(-2).y(-1). The weathering index (Re). calculated from molecular ratios of dissolved cations and silica in the river, suggests an intense silicate weathering leading to kaolinite-gibbsite precipitation in the weathering covers. The intense SWR and CCR could be due to the combination of high runoff and temperature along with the thickness and nature of the weathering cover. The comparison of silicate weathering fluxes with other watersheds reveals that under similar morpho-climatic settings basalt weathering would be 2.5 times higher than the granite-gneissic rocks. (C) 2012 Elsevier B.V. All rights reserved.

Specific Adsorption of Trace Amounts of Calcium and Strontium by Hydrous Oxides of Iron and Aluminum1

Freshly prepared Fe and Al hydrous oxide gels and the amorphous product of heating gibbsite selectively adsorbed traces of Ca and Sr from solutions containing a large excess (∼1M) of NaNO3. The fraction of the added Ca (Sr) adsorbed depended principally on the suspension pH, the amount of solid present, and to a lesser extent on the NaNO3 concentration. Significant Ca and Sr adsorption occurred on the Fe and Al gels, and heated gibbsite, at pH values below the points of zero charge (8.1, 9.4, and 8.3±0.1, respectively), indicating specific adsorption. The pH (± 0.10) at which 50% of the Ca was adsorbed (pH50) occurred at pH 7.15 for the Fe gel (0.093M Fe), 8.35 for the Al gel (0.093M Al), and 6.70 for the heated gibbsite (0.181M Al); for Sr, the pH50 values were 7.10, 9.00, and 6.45, respectively. For the Fe gel and heated gibbsite, an empirical model based on the law of mass action described the pH dependence of adsorption reasonably well and suggested that for each Ca or Sr fraction adsorbed, approximately one proton was released. Failure of the Al gel to fit this model may have resulted from its rapid aging.

The lateritic profile of Balkouin, Burkina Faso: geochemistry, mineralogy and genesis

This study reports on the geochemical and mineralogical characterization of a lateritic profile cropping out in the Balkouin area, Central Burkina Faso, aimed at obtaining a better understanding of the processes responsible for the formation of the laterite itself and the constraints to its development. The lateritic profile rests on a Paleoproterozoic basement mostly composed of granodioritic rocks related to the Eburnean magmatic cycle passing upwards to saprolite and consists of four main composite horizons (bottom to top): kaolinite and clay-rich horizons, mottled laterite and iron-rich duricrust. In order to achieve such a goal, a multi-disciplinary analytical approach was adopted, which includes inductively coupled plasma (ICP) atomic emission and mass spectrometries (ICP-AES and ICP-MS respectively), X-ray powder diffraction (XRPD), scanning electron microscopy with energy dispersive spectrometry (SEM-EDS) and micro-Raman spectroscopy.

The geochemical data, and particularly the immobile elements distribution and REE patterns, show that the Balkouin laterite is the product of an in situ lateritization process that involved a strong depletion of the more soluble elements (K, Mg, Ca, Na, Rb, Sr and Ba) and an enrichment in Fe; Si was also removed, particularly in the uppermost horizons. All along the profile the change in composition is coupled with important changes in mineralogy. In particular, the saprolite is characterized by occurrence of abundant albitic plagioclase, quartz and nontronite; kaolinite is apparently absent. The transition to the overlying lateritic profile marks the breakdown of plagioclase and nontronite, thus allowing kaolinite to become one of the major components upwards, together with goethite and quartz. The upper part of the profile is strongly enriched in hematite (+ kaolinite). Ti oxides (at least in part as anatase) and apatite are typical accessory phases, while free aluminum hydroxides are notably absent. Mass change calculations emphasize the extent of the mass loss, which exceeds 50 wt% (and often 70 wt%) for almost all horizons; only Fe was significantly concentrated in the residual system.

The geochemical and mineralogical features suggest that the lateritic profile is the product of a continuous process that gradually developed from the bedrock upwards, in agreement with the Schellmann classic genetic model. The laterite formation must have occurred at low pH (? 4.5) and high Eh (? 0.4) values, i.e., under acidic and oxidizing environments, which allowed strongly selective leaching conditions. The lack of gibbsite and bohemite is in agreement with the compositional data: the occurrence of quartz (± amorphous silica) all along the profile was an inhibiting factor for the formation of free aluminum hydroxides.

Do spectral gamma ray data really reflect humid-arid palaeoclimates? A test from the Palaeogene Interbasaltic weathered horizons at the Giant’s Causeway, N.Ireland

Since 1999, the rapid, inexpensive and non-destructive use of Th/K and Th/U ratios from spectral gamma ray measurements have been used as a proxy for changes in palaeo-hinterland weathering. This model is tested here by analysis of in situ palaeoweathering horizons where clay mineral contents are well-known. A residual palaeoweathered horizon of Palaeogene laterite (developed on basalt) has been logged at 14 locations across N. Ireland using spectral gamma ray detectors. The results are compared to published elemental and mineralogical data. While the model of K and U loss during the early stages of weathering to smectite and kaolinite is supported, the formation (during progressively more advanced weathering) of gibbsite and iron oxides has reversed the predicted pattern and caused U and Th retention in the weathering profile. The severity (duration, humidity) of weathering and palaeoweathering may be estimated using Th/K ratios as a proxy. The use of Th/U ratios is more problematic should detrital gibbsite (or similar clays) or iron oxides be detected. Mineralogical analysis is needed in order to evaluate the hosts for K, U and Th: nonetheless, the spectral gamma ray machine offers a real-time, inexpensive and effective tool for the preliminary or conjunctive assessment of degrees of weathering or palaeoweathering.

Provenance, Sedimentation and Geochemistry' of the Modern Sediments of time Mud Banks Off the Centrai Keraia Coast, India

This thesis is an attempt to Provenence, Sedimentetion and Geochemistry of the Modern Sediments of the Mud Banks off the Central Kerela Coast, India. In the present doctoral work, an attempt has been made to study in detail the mud banks of central Kerala, i.e. of Narakkal, Saudi and Purakkad areas which are reported as permanent mud banks, since olden days. The studies have been conducted during the years 1985 and 1986. The important findings of the study is stated as clay mineralogical studies of the rivers, lake and mud bank sediments reveal that the dominant clay mineral is kaolinite followed by montmorillonite, illite and gibbsite. Geochemical analysis of the Vembanad lake and mud bank sediments show that the iron and manganese are widely distributed both in the lake and mud bank sediments

Influence of aluminum hydroxide on potassium release from two Colombian soils

The effect of sesquioxides on the mechanisms of chemical reactions that govern the transformation between exchangeable potassium (Kex) and non-exchangeable K (Knex) was studied on acid tropical soils from Colombia: Caribia with predominantly 2 : 1 clay minerals and High Terrace with predominantly 1 : 1 clay minerals and sesquioxides. Illite and vermiculite are the main clay minerals in Caribia followed by kaolinite, gibbsite, and plagioclase, and kaolinite is the major clay mineral in High Terrace followed by hydroxyl-Al interlayered vermiculite, quartz, and pyrophyllite. The soils have 1.8 and 0.5% of K2O, respectively. They were used either untreated or prepared by adding AlCl3 and NaOH, which produced aluminum hydroxide. The soils were percolated continuously with 10mM NH4OAc at pH 7.0 and 10 mM CaCl2 at pH 5.8 for 120 h at 6 mL h(-1) to examine the release of Kex and Knex. In the untreated soils, NH4+ and Ca-2(+) released the same amounts of Kex from Caribia, whereas NH4+ released about twice as much Kex as Ca2+ from High Terrace. This study proposes that the small ionic size of NH4+ (0.54nm) enables it to enter more easily into the K sites at the broken edges of the kaolinite where Ca2+ (0.96 nm) cannot have access. As expected for a soil dominated by 2 : 1 clay minerals, Ca2+ caused Knex to be released from Caribia with no release by NH4+. No Knex was released by either ion from High Terrace. After treatment with aluminum hydroxide, K release from the exchangeable fraction was reduced in Caribia due to the blocking of the exchange sites but release of Knex was not affected. The treatment increased the amount of Kex released from the High Terrace soil and the release of Knex remained negligible although with Ca2+ the distinction between Kex and Knex was unclear. The increase in Kex was attributed to the initially acidic conditions produced by adding AlCl3 which may have dissolved interlayered aluminum hydroxide from the vermiculite present, thus exposing trapped K as exchangeable K. The subsequent precipitation of aluminum hydroxide when NaOH was added did not interfere with the release of this K, and so was probably formed mostly on the surface of the dominant kaolinite. Measurement of availability of K by standard methods using NH4 salts could result in overestimates in High Terrace and this may be a more general shortcoming of the methods in kaolinitic soils.