From Plinthic Acrisols to Plinthosols and Gleysols: iron and groundwater dynamics in the tertiary sediments of the upper Amazon basin

Topography has been reported to be the major factor ruling the spatial distribution of Acrisols, Plinthosols and Gleysols on the seasonally flooded, low elevation plateaux of the upper Amazon basin occupied by Tertiary (Ica & Solimoes) sediments. In this study, detailed morphological and mineralogical investigations conducted in a representative 25-ha site were combined with hydro-geochemical data to relate the vertical and lateral soil differentiations observed to the hydro-geological history of that part of the basin. As a result of the uplift of the Andes, several cuts in the extensive Tertiary marshlands have formed, at first, slightly incised plateaux of low elevation. There, weathering under hot and humid climates would have generated a reddish, freely drained and bioturbated topsoil layer and the vertical differentiation in subsoil sediments of a plinthite over an iron-depleted mottled clay. The second episode of soil differentiation is linked to the replacement of the forest by a savannah under the drier climates of the late Pleistocene, which favours surface runoff and the infill of the incisions by fine particles. This infill, combined with the return to the present humid climate, has then enabled the local groundwater to rise on the plateaux and to generate episaturation at the topsoil/subsoil transition close to the depressions. Nowadays, ferrous iron is released from the partly iron-depleted topsoil weathering front at high water levels during the rainy seasons. It moves from footslope to low-lying positions and from top to bottom in the soil profile according to the groundwater dynamics. The present general trend is thus to the lateral export of iron at high water levels due to subsurface and overland flows, its vertical transfer during the recession of the groundwater and accumulation in a nodular plinthite. In the latter, ferrous iron is adsorbed onto its softest iron masses where it feeds the neoformation of ferrihydrite that rapidly dehydrates into haematite.

Chemical vapor deposition of multi-walled carbon nanotubes from nickel/yttria-stabilized zirconia catalysts

Multi-walled carbon nanotubes (MWNT) were produced by chemical vapor deposition using yttria-stabilized zirconia/nickel (YSZ/Ni) catalysts. The catalysts were obtained by a liquid mixture technique that resulted in fine dispersed nanoparticles of NiO supported in the YSZ matrix. High quality MWNT having smooth walls, few defects, and low amounts of by-products such as amorphous carbon were obtained, even from catalysts with large Ni concentrations (> 50 wt.%). By adjusting the experimental parameters, such as flux of the carbon precursor (ethylene) and Ni concentration, both the MWNT morphology and the process yield could be controlled. The resulting YSZ/Ni/MWNT composites can be interesting due to their mixed ionic-electronic transport properties, which could be useful in electrochemical applications.

Serum iron and plasma fibrinogen concentrations as indicators of systemic inflammatory diseases in horses

Background: Detection of systemic inflammation, which is important for proper diagnosis and prompt treatment, can be challenging.Hypothesis: Measurement of plasma iron concentration is a sensitive method for detecting systemic inflammation in horses compared with measurements of plasma Fibrinogen concentration, a traditional marker for inflammation in the horse.Animals: Ninety-seven horses hospitalized with diseases causing systemic inflammation, 22 horses with localized inflammation, and 12 clinically normal horses were included in this study.Methods: A retrospective study was made on hospitalized horses that had both plasma iron and fibrinogen concentrations measured on hospital admission.Results: Plasma iron concentration was lower in horses with systemic inflammation (64 +/- 45 mu g/dL) than the reference interval minimum (105 mu g/dL) and were significantly lower (P = .001) than the value in a group of horses with local inflammation (123 +/- 45 mu g/dL) and in healthy transported horses (143 +/- 29 mu g/dL). Low plasma iron and high fibrinogen concentrations were both sensitive indicators of systemic inflammation in horses with sensitivity of 90 and 82%, respectively. There was a similar correlation between either continued decreases in iron concentration (R-sp of 0.239) or increases in fibrinogen concentration (R-sp of 0.280) during hospitalization and a worse prognosis.Conclusions and Clinical Importance: Measurement of plasma iron concentration better reflected acute inflammation than did fibrinogen concentration.

Sintering of zirconia composites obtained by slip casting

Composites containing a matrix of nanometric Ce-stabilized zirconia with an addition of micrometric monoclinic zirconia were processed by slip casting and sintered at a relatively low temperature. The ratio between nanometric and micrometric particles was determined according to the viscosity of the suspensions and the final density of the pellets. An optimum amount of micrometric particles was necessary to achieve improved suspension dispersion and higher pellet density. The amount of deflocculant in the suspensions containing the mixture of micrometric and nanometric particles was optimized by viscosity measurements. The pellets were characterized by dilatometry, Hg porosimetry, density measurement (the Archimedes method) and scanning electron microscopy. Despite the low green density obtained (35-38% of the theoretical density), densities as high as 97.5% were achieved after sintering. (C) 2001 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Zirconia needles synthesized inside hexagonal swollen liquid crystals

We report the synthesis of zirconia microneedles by the direct nucleation of particles inside a hexagonal swollen liquid crystal (SLC) (cell parameter a = 27 nm) prepared by mixing with the proper ratio, an aqueous solution of sulfated zirconium colloids, a cationic surfactant (cetylpyridinium chloride), cychlohexane as swelling agent with an oil over water ratio of 2.5 (vol.), and 1-pentanol as cosurfactant. After a slow crystallogenesis that can be enhanced by an initial induction step under moderate temperature, particles in the centimeter range can be obtained, with a very high shape ratio (over 100). These particles are made of crystalline octahydrate zirconium oxychloride containing pores of 20 nm diameter, aligned along the main axis of the liquid crystal, as the fingerprint of the oil cylinders present in the hexagonal phase. The morphology of these particles confirms that the shaping mechanism is based on true liquid crystal templating (TLCT). Further thermal treatment of these particles, after extraction from the SLC, leads to the crystallization of zirconia with the same needlelike morphology as the zirconium oxychloride.

Effect of iron on inhibition of acid demineralisation of bovine dental enamel in vitro

Objectives: Iron ions (Fe2+) have been shown to be cariostatic in many studies particularly by their ability to reduce bacterial metabolism. Nevertheless, the role of iron ions on dissolution of enamel is unexplored. The aim of the present study was therefore to investigate the protective effect of increasing concentrations (0-120 mmol/L) of Fe2+ on the dissolution of enamel.Design: Enamel powder was subjected to acetic acid made with increasing concentrations with respect to FeSO4 center dot 7H(2)O. In order to determine the amount of enamel dissolved, the phosphate released in the medium was analysed spectrophotometrically using the Fiske-Subarrow method. Data were tested using Kruskall-Wall and Dunn's tests (p < 0.05). The degree of protection was found to approach maximum at about 15 mmol/L Fe2+. Higher concentrations of Fe2+ did not have an extra effect on inhibition of dissolution of enamel powder. In the next step, the protective effect of 15 mmol/L Fe2+ against mineral dissolution of the bovine enamel was evaluated using a simple abiotic model system. Enamel blocks were exposed to a sequence of seven plastic vials, each containing 1 mL of 10 mmol/L acetic acid. The acid in vial 4 was made 15 mmol/L with respect to FeSO4 center dot 7H(2)O. The mineral dissolved during each challenge was thus determined by phosphate released as described above. Data were tested using two-way ANOVA (p < 0.05). Results: Lower demineralisation (around 45%) was found in vial 4 (with Fe) that continued stable until vial 7.Conclusions: Thus, our data suggest that Fe2+, can be effective on inhibition of dissolution of enamel and that this effect may be durable. (c) 2006 Elsevier Ltd. All rights reserved.

X-ray reflectivity of zirconia based sol-gel coatings on borosilicate glasses

In this work the technique of X-ray reflectometry was applied to study zirconiumsulfate films deposited by sol-gel dip-coating process on a borosilicate glass surface. The influence of withdrawal speed and temperature of thermal treatment on the film structure are analyzed. The thermal evolution of the density and thickness of the film was compared with these properties measured for a monolithic xerogel by helium picnometry and thermomechanical analysis. The fitting of experimental curves by classical reflectivity model showed the presence of an additional layer at the top surface of the coating. Layer thickness increases with increase of withdrawal speed in agreement with the Landau-Levich model. The apparent and real densities are similar for coatings fired below 400 degrees C, which shows that the films are free of pores. The shrinkage during firing is anisotropic, occurring essentially perpendicular to the coating surface. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Structural and magnetic transformation of monodispersed iron oxide particles in a reducing atmosphere

Uniform metal iron ellipsoidal particles of around 200 nm in length were obtained by reduction and passivation of alumina-coated alpha-Fe2O3 (hematite) particles under different conditions of temperature and hydrogen flow rate. The monodispersed hematite particles were prepared by the controlled hydrolysis of ferric sulfate and further coated with a homogeneous thin layer of Al2O3 by careful selection of the experimental conditions, mainly pH and aluminum salt concentration. The reduction mechanism of alpha-Fe2O3 into alpha-Fe was followed by x-ray and electron diffraction, and also by the measurements of the irreversible magnetic susceptibility. The transformation was found to be topotactic with the [001] direction of hematite particles, which lies along the long axis of the particles, becoming the [111] direction of magnetite and finally the [111] direction of metal iron. Temperature and hydrogen flow rate during the reduction have been found to be important parameters, which determine not only the degree of reduction but also the crystallite size of the final particles. Magnetic characterization of the samples shows that the only parameters affected by the crystallite size are the saturation magnetization and magnetic time-dependence effect, i.e., activation volume. (C) 2002 American Institute of Physics.

Small-angle X-ray scattering and X-ray absorption near-edge structure study of iron-doped siloxane-polyoxyethylene nanocomposites

The local and medium-range structures of siloxane-POE hybrids doped with Fe(III) ions and prepared by the sol-gel process were investigated by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) and small-angle X-ray scattering (SAXS), respectively. The experimental results show that the structure of these composites depends on the doping level. EXAFS data reveal that, for low doping levels ([O]/[Fe] > 40, oxygens being of the ether-type of the POE chains), Fe(III) ions are surrounded essentially by a shell of chlorine atoms, suggesting the formation of FeCl4- anions. At high doping levels ([O]/[Fe] < 20), Fe(III) ions interacts mainly with oxygen atoms and form FeOx species. The relative proportion of FeOx species increases with iron concentration, this result being consistent with the results of SAXS measurements showing that increasing iron doping induces the formation of iron-rich nanodomains embedded in the polymer matrix.

Structural features of phosphate and sulfate modified zirconia prepared by sol-gel route

This paper describes the effect of sulfate, phosphate and nitrate complexing ligands on the structural features of amorphous xerogels and on the crystallization of metastable zirconia phases during the xerogel-ceramic conversion. Powdered samples were prepared by a sol-gel route using zirconyl chloride precursors chemically modified by complexing ligands. The structural evolution of ZrO2 phases as function of firing temperature was analyzed by XRPD, EXAFS and P-13 NMR/MAS. The experimental results show the formation of metastable t-ZrO2 during the low firing temperature of xerogels modified by sulfate or phosphate groups. The martensitic tetragonal-monoclinic transformation occurs during desorption of sulfate groups. The largest temperature interval of stability of metastable tetragonal zirconia was observed for phosphate-modified xerogels.

Kinetics and mechanism of the induced redox reaction of [Ni(cyclam)](2+) promoted by SO5 center dot-

Oxidation of [Ni(cyclam)](2+), cyclam = 1,4,8,11-tetraazacyclotetradecane, accelerated by sulfur dioxide, was studied spectrophotometrically by following the formation of [Ni(cyclam)](3+) under the conditions: [Ni(cyclam)](2+) = 6.0 x 10(-3) M; initial [Ni(cyclam)](3+) = 8.0 x 10(-6) M; [cyclam] = 6.0 x 10(-3) M; [SO2] = (1.0-5.0) x 10(-4) M and 1.0 M perchloric acid in oxygen saturated solutions at 25.0 degrees C and ionic strength = 1.0 M. The oxidation reaction exhibits autocatalytic behavior in which the induction period depends on the initial Ni(III) concentration. A kinetic study of the reduction of Ni(III) by SO2 under anaerobic conditions, and the oxidation of Ni(II), showed that the rate-determining step involves reduction of Ni(III) by SO2 to produce the SO3.- radical, which rapidly reacts with dissolved oxygen to produce SO5.- and rapidly oxidizes Ni(II). The results clearly show a redox cycling process which depends on the balance of SO2 and oxygen concentrations in solution.

Polymeric organic-inorganic hybrid material containing iron(III) porphyrin using sol-gel process

Here we describe the preparation of iron(II) porphyrinosilica in a simple one-pot reaction, where the -SO2Cl groups present in the phenyl rings of FeTDCSPP+ react with 3-aminopropyltriethoxysilane and tetraethoxysilane in the presence of a nitrogenous base, leading to iron(III) porphyrinosilica. In this same procedure, molecular cavities containing regularly spaced functional groups are created through the molecular imprinting technique, in which the nitrogenous base coordinated to the iron(III) porphyrin serves as a template. The removal of such template in a Soxhlet extractor leads to a cavity with the same shape and size as the nitrogenous base, enabling the construction of shape-selective catalysts mimicking cytochrome P-450. Five different imprinting molecules have been used: imidazole, 1-methylimidazole, 2-methylbenzimidazole, 4-phenylimidazole and miconazole and ultra-violet/visible absorption spectroscopy, thermogravimetric analysis and electron paramagnetic resonance carried out. (C) 1999 Elsevier B.V. B.V. All rights reserved.