Al-substituted goethites were prepared by rapid oxidation of mixed FeCl2-AlCl3 solutions at pH 6.8 in the presence of CO2 at 25°C. A combination of Al substitution and adsorption of CO2 reduced crystal size (except for an increase at small additions of Al) and produced unusual thin, porous particles. Product goethites had surface areas up to 283 m2/g and unit-cell expansions induced by hydration. Substitution of Al for Fe reduced the 111 spacing and increased infrared OH-bending vibrational frequencies. Al substitution split the goethite dehydroxylation endotherm during differential thermal analysis into a doublet and increased the temperature of all reactions. Both cold and hot alkali solutions dissolved Al from the goethite structure.

After drying the product in vacuo at 110°C. X-ray powder diffraction data indicated minimal deviation from Vegard's law for the goethite-diaspore solid solution up to about 30 mole % Al substitution. Goethite prepared in the presence of 40 mole % Al had a 111 spacing of 2.403 Å corresponding to 36 mole % structural Al if Vegard's law was obeyed. Rapid oxidation of mixed FeCl2-AlCl3 solutions appears to be conducive to a higher degree of Al substitution in goethite than alkaline aging of hydroxy-Fe(III)-Al coprecipitates.

Sixty-five bauxite samples of different ages and origins were studied by scanning electron microscopy. Only broken surfaces of the specimens were investigated. Size and form of individual crystals and of grain aggregates were studied as were different types of microtextures and space-fillers.

Grain size varies from 0.05 μm to 1 mm. Smallest is the grain size of young karstic bauxite deposits that is explained by a physicochemical retardation effect of the carbonate environment. Significant differences were found by comparing the space-filling of karstic and lateritic bauxite deposits. High-level and low-level lateritic deposits show differences as well.

A combined use of macroscopic observations, petrographie microscopy, electron microprobe, SEM, and TЕM furnishes the best clues for any genetic interpretation of bauxites. SEM studies are useful in solving technological problems of bauxite processing.

Sedimentologic zones that are differentiated by changes in lithology, mineralogy, chemical composition, and crystal morphology observable in scanning electron micrographs occur in Missouri high-alumina clay deposits. These properties and changes suggest that the high-alumina materials originated from Pennsylvanian-age, paludal sediments deposited in depressions underlying Paleozoic carbonate rocks. Alumina was relatively enriched in zones of the deposits by leaching of silica and of alkali and alkaline earth metals from the sediments. The most intense leaching occurred on the highest parts of the Ozark Dome.

Diaspore is the predominant high-alumina mineral. Boehmite, although far less abundant than diapsore, may have paragenetically preceded diaspore in some deposits. Chlorite, presumably an Al-rich variety because the content of MgO is typically <0.5%, is also present. Li, which is sporadically present, is inferred to have accumulated in the chlorite which may be a proto-variety of cookeite. Because Li+ and Al3+ are similar in size, Li is inferred to have accompanied Al as a resistate element in contrast to K and Na which were leached from parent phyllosilicates.

The solubilities of HCl-treated samples of corundum, gibbsite, boehmite, and diaspore in aqueous solutions at 298 K and one atmosphere pressure were determined from undersaturated and supersaturated initial conditions. Solution characteristics at apparent equilibrium were measured and used to calculate equilibrium constants (Kr) for mineral dissolution reactions:

$$\begin{array}{l} A{l_2}{O_3}\left( {corundum} \right) + 3{H^ + } = A{l^3} + 1.5\,{H_2}O,\\ Al{\left( {OH} \right)_3}\left( {gibbsite} \right) + 3{H^ + } = A{l^3} + 3\,{H_2}O,\\ and\\ AlOOH\left( {boehmite\,or\,diaspore} \right) + 3{H^ + } = A{l^3} + 2{H_2}O, \end{array}$$

During the epigenetic alteration of boehmitic karstic bauxite in the Vlasenica region of Yugoslavia, which was caused by siliceous water descending through the deposit by means of cracks, fissures, etc., oolites were less altered compared with the coexisting matrix material, which was intensely kaolinized. The following zonal alteration pattern of the oolites was identified: a diaspore enrichment zone, followed by a diaspore-boehmite enrichment zone, and then the original bauxite. Considering this alteration pattern and that determined previously for the matrix material, the following overall pattern of alteration was established: a kaolinite-diaspore zone, followed by a boehmite-diaspore zone, and then the original bauxite. The alteration solutions reacted with the bauxite to form solution-matrix and solution-oolite subsystems, which were characterized by different types of diffusion and geochemistry.

In the kaolinite-diaspore zone Si-metasomatism kaolinized the matrix, and excess Al partly migrated into the oolites, forming diaspore, and outward into the bauxite. The latter Al-remobilization resulted in a transition zone, in which new boehmite was formed in both the matrix and the oolites, and diaspore only in the oolites. Thermodynamic models of oolites and whole bauxite alterations were established, on the basis of stability diagrams calculated for the mineral assemblages of both the oolites and the matrix, in the alteration zones and in the deposit as a whole. Based on these models, the genesis of the diaspore and the relationship of diaspore-boehmite-kaolinite assemblages in natural systems at low temperature and low pressure can be described.

This paper describes in detail phosphate minerals occurring in refractory clays of Missouri and their effect on the refractory degree of the clays. The minerals identified include carbonate-fluorapatite (francolite), crandallite, goyazite, wavellite, variscite and strengite. It is emphasized that these phosphates occur only in local isolated concentrations, and not generally in Missouri refractory clays.

The Missouri fireclay region comprises 2 districts, northern and southern, separated by the Missouri River. In this region, clay constitutes a major part of the Lower Pennsylvanian Cheltenham Formation. The original Cheltenham mud was an argillic residue derived from leaching and dissolution of pre-Pennsylvanian carbonates. The mud accumulated on a karstic erosion surface truncating the pre-Cheltenham rocks. Fireclays of the northern district consist mainly of poorly ordered kaolinite, with variable but minor amounts of illite, chlorite and fine-grained detrital quartz. Clays of the southern district were subjected to extreme leaching that produced well-ordered kaolinite flint clays. Local desilication formed pockets of diaspore, or more commonly, kaolinite, with oolite-like nubs or burls of diaspore (“burley” clay).

The phosphate-bearing materials have been studied by X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectral analysis (SEM-EDS) and chemical analysis. Calcian goyazite was identified in a sample of diaspore, and francolite in a sample of flint clay. A veinlet of wavellite occurs in flint clay at one locality, and a veinlet of variscite-strengite at another locality.

The Missouri flint-clay-hosted francolite could not have formed in the same manner as marine francolite. The evidence suggests that the Cheltenham francolite precipitated from ion complexes in pore water, nearly simultaneously with crystallization of kaolinite flint clay from an alumina-silica gel. Calcian goyazite is an early diagenetic addition to its diaspore host. The wavellite and variscite-strengite veinlets are secondary, precipitated from ion complexes in ground water percolating along cracks in the flint clay. The flint clay host of the variscite-strengite veinlet contains strontian crandallite. All of the phosphates contain significant amounts of strontium. The source of P, Ca and Sr was the marine carbonates. Dissolution of these carbonates produced the argillic residue that became the primordial Cheltenham paludal mud, which ultimately altered to fireclay.

Preliminary firing tests show that the presence of phosphates lowers fusion temperature. However, it is not clear whether poor refractoriness is due to the presence of phosphates, per se, or to Ca, Sr and other alkaline elements present in the phosphates.

The collector for separating diasporic bauxite serves as a type of flotation reagent by adsorbing selectively on diaspore to make it hydrophobic enough to separate it from the aluminosilicates. Although the flotation process is considered economical in the desilication of Chinese diasporic bauxite, the existing collectors fail to separate these ores because of their poor adsorption selectivity over other minerals. The present study was an attempt to seek a collector for selective flotation of diaspore over aluminosilicates. A novel carboxyl hydroxamic acid compound, 2,2-bis(hydroxycarbamoyl) decanoic acid (BHDA), was designed and synthesized, and the flotation behavior of diaspore, kaolinite, and illite was investigated by flotation tests with BHDA. The interactions between the BHDA and the minerals were also explored by Fourier-transform infrared spectroscopy (FTIR), zeta-potential measurement, and density functional theory (DFT) calculation. Using BHDA as the collector, the pulp pH value affected the floatability of diaspore significantly while the floatability of kaolinite or illite was unaffected or only slightly affected. The dosage of BHDA had little effect on the floatability of the three minerals. The greatest difference in floatability between diaspore and aluminosilicates occurred at mid-range pulp pH (7). Large shifts in characteristic absorption peaks and new absorption peaks were observed for BHDA-treated diaspore but were absent from BHDA-treated aluminosilicates. The change in the negative zeta potential of diaspore was also greater than those of aluminosilicates in the presence of BHDA. The O atoms in the carboxyl and hydroxycarbamoyl of BHDA have highly negative charges, and favorable stereo conditions existed to form five- or six-membered rings, resulting in their coordination with the Al atoms of diaspore, leading to chemisorption in chelate rings; the adsorption of BHDA on kaolinite or illite, on the other hand, was mainly physical in nature. The BHDA was, therefore, highly selective in the flotation between diaspore and aluminosilicates and possibly suitable for the separation of diasporic bauxite.

Unusual corundum-bearing rocks occur in the Bond Range, northern Tasmania, in a hydrothermally altered Cambrian quartz porphyry. The assemblage exhibits quartz and corundum in mutual contact, a rare phenomenon, in association with andalusite, pyrophyllite, diaspore and other minerals. This metastable assemblage apparently resulted from advanced argillic alteration at moderate temperature and low pressure, followed by rapid depressurisation accompanying boiling of hydrothermal, granite-derived fluids. This corundum occurrence appears to be unrelated to the sapphires in placer deposits in Tasmania.

Ab initio total energy calculations based on the local density approximation (LDA) and using a conjugate-gradient solver for the Kohn-Sham equations have been performed for cordierite, brucite, (Mg(OH)2) and diaspore (AlOOH). The calculated fractional coordinates of all structures are in good agreement with experimental diffraction data. The angle of the non-linear hydrogen bond in diaspore is reproduced well. The Raman active OH stretching frequency in brucite has been calculated using the frozen phonon approach and the calculated stretching frequency is in very good agreement with the observed value. The energetically most favourable calculated orientation of the proton-proton vector of an H2O molecule incorporated in the structural channels of cordierite agrees with findings deduced from spectroscopic data, and the calculated energy of hydration is in reasonable agreement with calorimetric data. It is therefore concluded that ab initio total energy calculations can confidently be used to predict properties of hydrogen bonded structures, which is difficult with conventional parameterized static lattice energy minimization calculations. An extension to the model is necessary to improve the agreement of the predicted to the observed lattice parameters for small structures.

Swartzia langsdorffii seeds have recalcitrant characteristics. Nonetheless, dispersal begins in the month with the lowest precipitation in the studied region, which could lead to seed death by desiccation. Therefore, the objectives of this study were: (1) to characterize the physiological behaviour of S. langsdorffii seeds related to their desiccation sensitivity/tolerance; and (2) to assess the morphophysiological characteristics that enable the seeds to remain viable after dispersal. Fruits and seeds were subjected to biometric evaluation and the anatomical and ultrastructural features of the seeds were determined. Field assessments were performed to determine the capacity of the seeds to maintain viability and to verify the relation between seed viability, diaspore water content and environmental variables. Seeds of this species were found to be recalcitrant and showed pores distributed throughout the seed coat, and contained a large number of stomata in the hypocotyl–radicle axis epidermis. Moreover, phenolic compounds were found throughout the radicle region. Seeds remained viable in the soil for up to 7 months after dispersal without a significant decrease in water content, despite the low precipitation and soil water content. Radicle protrusion began 5 months after dispersal and coincided with partial fruit decomposition at the beginning of the rainy season. Thus, the possible microclimate created by the pericarp, with the moisture content of the aril and the soil, the presence of the structures in the axis, such as the pores and stomata, the chemical composition and the morphology of S. langsdorffii seeds could favour maintenance of their viability until the beginning of the rainy season.

Rain forests at Los Tuxtlas are islands surrounded by anthropogenic vegetation containing invasive species. Epizoochory is an important dispersal syndrome among invasive species but ecological studies are scant. In order to evaluate the movement of epizoochore diaspores into the mature forest, we selected two abundant secondary herbs with contrasting diaspore morphology, and five dispersers with different pelage type. We used stuffed mammals as a dummy and passed them through patches of these two plant species, counting the number of adhered diaspores. For dispersal into the forest, diaspores were manually adhered to dispersers, these were pulled along 100-m forest transects, counting the number of diaspores remaining at distance intervals. We observed the highest amount of detachment in the first 20 m of the forest edge. For Desmodium incanum diaspores with sticky hairs, adhesion to dispersers showed no differences among pelage types, therefore dispersal is determined mainly by diaspore detachment. Dispersers with long pelage (Didelphis marsupialis, Nasua narica and Procyon lotor) move diaspores for shorter distances, while dispersers with short pelage (Silvilagus floridanus and Philander opossum) are more likely to move diaspores for longer distances. In Pavonia schiedeana more diaspores (seeds with spines and hooks) were attached and remained attached on dispersers with long and thick pelage. Mean distance travelled for P. schiedeana diaspores varied between 11 and 2700 m. In D. incanum the distance travelled did not exceed 500 m. Based on comparisons between dispersal patterns and on ecological data of these two plant species and their potential dispersers, P. schiedeana has a higher probability of invading the forest and finding suitable habitats for establishment than D. incanum.

This study describes the fruiting phenology of woody plants and their dispersal syndromes in caatinga (semi-arid region in the northeast of Brazil). The fruiting phenology of 42 species with different dispersal modes and life-forms was followed over a period of 1 y. Animal dispersal was the most commonly observed dispersal mode (36%), followed by anemochory (33%), ballistic dispersal (19%) and barochory (12%). Overall, a greater number of species fruited during the rainy season. Zoochorous species were the most representative in the rainy season, whereas anemochorous species predominated during the dry season. Five different life-forms were observed, and the occurrence of dispersal modes was discussed for each of them. In the caatinga plant community studied the patterns of life-forms, fruiting phenology and seed dispersal syndromes were similar to other tropical seasonal ecosystems.

Este trabalho teve como objetivo principal descrever como se comportam as espécies de caatinga (região semi-árida do Nordeste brasileiro) com relação ao modo de dispersão durante as estações seca e chuvosa. Foram observados também os modos de dispersão apresentados em cada forma de vida. A fenofase de frutificação foi acompanhada em 10 indivíduos de 42 espécies durante um intervalo de um ano. A zoocoria representou o modo de dispersão mais observado (36%), seguido da anemocoria (33%), balística (19%) e barocoria (12%). Um maior número de espécies frutificou durante a estação de chuvas, sendo a zoocoria mais representativa nesta estação, enquanto que a anemocoria foi mais representativa na época de estiagem. Foram observadas várias formas de vida, discutindo-se o modo de dispersão em cada uma delas. Constatou-se que as espécies de caatinga estudadas encontram-se dentro dos padrões gerais de época de dispersão dos diásporos e representatividade das síndromes de dispersão observados em outros ecossistemas com sazonalidade.