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.

Materials and concepts for CO2 lean ironmaking by pyroelectrolysis

The main purpose of this PhD thesis was to provide convincing demonstration for a breakthrough concept of pyroelectrolysis at laboratory scale. One attempted to identify fundamental objections and/or the most critical constraints, to propose workable concepts for the overall process and for feasible electrodes, and to establish the main requirements on a clearer basis. The main effort was dedicated to studying suitable anode materials to be developed for large scale industrial units with molten silicate electrolyte. This concept relies on consumable anodes based on iron oxides, and a liquid Fe cathode, separated from the refractory materials by a freeze lining (solid) layer. In addition, one assessed an alternative concept of pyroelectrolysis with electron blocking membranes, and developed a prototype at small laboratory scale. The main composition of the molten electrolyte was based on a magnesium aluminosilicate composition, with minimum liquidus temperature, and with different additions of iron oxide. One studied the dynamics of devitrification of these melts, crystallization of iron oxides or other phases, and Fe2+/Fe3+ redox changes under laser zone melting, at different pulling rates. These studies were intended to provide guidelines for dissolution of raw materials (iron oxides) in the molten electrolyte, to assess compatibility with magnetite based consumable anodes, and to account for thermal gradients or insufficient thermal management in large scale cells. Several laboratory scale prototype cells were used to demonstrate the concept of pyroelectrolysis with electron blocking, and to identify the most critical issues and challenges. Operation with and without electron blocking provided useful information on transport properties of the molten electrolyte (i.e., ionic and electronic conductivities), their expected dependence on anodic and cathodic overpotentials, limitations in faradaic efficiency, and onset of side electrochemical reactions. The concept of consumable anodes was based on magnetite and derived spinel compositions, for their expected redox stability at high temperatures, even under oxidising conditions. Spinel compositions were designed for prospective gains in refractoriness and redox stability in wider ranges of conditions (T, pO2 and anodic overpotentials), without excessive penalty for electrical conductivity, thermomechanical stability or other requirements. Composition changes were also mainly based on components of the molten aluminosilicate melt, to avoid undue contamination and to minimize the dissolution rate of consumable anodes. Additional changes in composition were intended for prospective pyroelectrolysis of Fe alloys, with additions of different elements (Cr, Mn, Ni, Ti).

Investigations on The Finite Size Effects of Some Inverse Spinels and Studies on Their Composites Based on Nitrile Rubber

Magnetism and magnetic materials have been an ever-attractive subject area for engineers and scientists alike because of its versatility in finding applications in useful devices. They find applications in a host of devices ranging from rudimentary devices like loud speakers to sophisticated gadgets like waveguides and Magnetic Random Access Memories (MRAM).The one and only material in the realm of magnetism that has been at the centre stage of applications is ferrites and in that spinel ferrites received the lions share as far as practical applications are concerned.It has been the endeavour of scientists and engineers to remove obsolescence and improve upon the existing so as to save energy and integrate in to various other systems. This has been the hallmark of material scientists and this has led to new materials and new technologies.In the field of ferrites too there has been considerable interest to devise new materials based on iron oxides and other compounds. This means synthesising ultra fine particles and tuning its properties to device new materials. There are various preparation techniques ranging from top- down to bottom-up approaches. This includes synthesising at molecular level, self assembling,gas based condensation. Iow temperature eo-precipitation, solgel process and high energy ball milling. Among these methods sol-gel process allows good control of the properties of ceramic materials. The advantage of this method includes processing at low temperature. mixing at the molecular level and fabrication of novel materials for various devices.Composites are materials. which combine the good qualities of one or more components. They can be prepared in situ or by mechanical means by the incorporation of fine particles in appropriate matrixes. The size of the magnetic powders as well as the nature of matrix affect the processability and other physical properties of the final product. These plastic/rubber magnets can in turn be useful for various applications in different devices. In applications involving ferrites at high frequencies, it is essential that the material possesses an appropriate dielectric permittivity and suitable magnetic permeability. This can be achieved by synthesizing rubber ferrite composites (RFC's). RFCs are very useful materials for microwave absorptions. Hence the synthesis of ferrites in the nanoregirne.investigations on their size effects on the structural, magnetic, and electrical properties and the incorporation of these ferrites into polymer matrixes assume significance.In the present study, nano particles of NiFe204, Li(!5Fe2S04 and Col-e-O, are prepared by sol gel method. By appropriate heat treatments, particles of different grain sizes are obtained. The structural, magnetic and electrical measurements are evaluated as a function of grain size and temperature. NiFel04 prepared in the ultrafine regime are then incorporated in nitrile rubber matrix. The incorporation was carried out according to a specific recipe and for various loadings of magnetic fillers. The cure characteristics, magnetic properties, electrical properties and mechanical properties of these elastomer blends are carried out. The electrical permittivity of all the rubber samples in the X - band are also conducted.

Reduction of arsenic uptake by lettuce with ferrous sulfate applied to contaminated soil

Soil contamination by arsenic (As) presents a hazard in many countries and there is a need for techniques to minimize As uptake by plants. A proposed in situ remediation method was tested by growing lettuce (Lactuca sativa L. cv. Kermit) in a greenhouse pot experiment on soil that contained 577 mg As kg(-1), taken from a former As smelter site. All combinations of iron (Fe) oxides, at concentrations of 0.00, 0.22, 0.54, and 1.09% (w/w), and lime, at concentrations of 0.00, 0.27, 0.68, and 1.36% (w/w), were tested in a factorial design. To create the treatments, field-moist soil, commercial-grade FeSO4, and ground agricultural lime were mixed and stored for one week, allowing Fe oxides to precipitate. Iron oxides gave highly significant (P < 0.001) reductions in lettuce As concentrations, down to 11% of the lettuce As concentration for untreated soil. For the Fe oxides and lime treatment combinations where soil pH was maintained nearly constant, the lettuce As concentration declined in an exponential relationship with increasing FeSO4 application rate and lettuce yield was almost unchanged. Iron oxides applied at a concentration of 1.09% did not give significantly lower lettuce As concentrations than the 0.54% treatment. Simultaneous addition of lime with FeSO4 was essential. Ferrous sulfate with insufficient lime lowered soil pH and caused mobilization of Al, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn. At the highest Fe oxide to lime ratios, Mn toxicity caused severe yield loss.

Sequential extraction and single-step cold-acid extraction: A feasibility study for use with freshwater-canal sediments

This investigation examines metal release from freshwater sediment using sequential extraction and single-step cold-acid leaching. The concentrations of Cd, Cr, Cu, Fe, Ni, Pb and Zn released using a standard 3-step sequential extraction (Rauret et al., 1999) are compared to those released using a 0.5 M HCl; leach. The results show that the three sediments behave in very different ways when subject to the same leaching experiments: the cold-acid extraction appears to remove higher relative concentrations of metals from the iron-rich sediment than from the other two sediments. Cold-acid extraction appears to be more effective at removing metals from sediments with crystalline iron oxides than the "reducible" step of the sequential extraction. The results show that a single-step acid leach can be just as effective as sequential extractions at removing metals from sediment and are a great deal less time-consuming.

Reduction of arsenic uptake by lettuce with ferrous sulfate applied to contaminated soil

Soil contamination by arsenic (As) presents a hazard in many countries and there is a need for techniques to minimize As uptake by plants. A proposed in situ remediation method was tested by growing lettuce (Lactuca sativa L. cv. Kermit) in a greenhouse pot experiment on soil that contained 577 mg As kg(-1), taken from a former As smelter site. All combinations of iron (Fe) oxides, at concentrations of 0.00, 0.22, 0.54, and 1.09% (w/w), and lime, at concentrations of 0.00, 0.27, 0.68, and 1.36% (w/w), were tested in a factorial design. To create the treatments, field-moist soil, commercial-grade FeSO4, and ground agricultural lime were mixed and stored for one week, allowing Fe oxides to precipitate. Iron oxides gave highly significant (P < 0.001) reductions in lettuce As concentrations, down to 11% of the lettuce As concentration for untreated soil. For the Fe oxides and lime treatment combinations where soil pH was maintained nearly constant, the lettuce As concentration declined in an exponential relationship with increasing FeSO4 application rate and lettuce yield was almost unchanged. Iron oxides applied at a concentration of 1.09% did not give significantly lower lettuce As concentrations than the 0.54% treatment. Simultaneous addition of lime with FeSO4 was essential. Ferrous sulfate with insufficient lime lowered soil pH and caused mobilization of Al, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn. At the highest Fe oxide to lime ratios, Mn toxicity caused severe yield loss.

Motivation, rationale and key results from the GERBILS Saharan dust measurement campaign

The Geostationary Earth Radiation Budget Intercomparison of Longwave and Shortwave radiation (GERBILS) was an observational field experiment over North Africa during June 2007. The campaign involved 10 flights by the FAAM BAe-146 research aircraft over southwestern parts of the Sahara Desert and coastal stretches of the Atlantic Ocean. Objectives of the GERBILS campaign included characterisation of mineral dust geographic distribution and physical and optical properties, assessment of the impact upon radiation, validation of satellite remote sensing retrievals, and validation of numerical weather prediction model forecasts of aerosol optical depths (AODs) and size distributions. We provide the motivation behind GERBILS and the experimental design and report the progress made in each of the objectives. We show that mineral dust in the region is relatively non-absorbing (mean single scattering albedo at 550 nm of 0.97) owing to the relatively small fraction of iron oxides present (1–3%), and that detailed spectral radiances are most accurately modelled using irregularly shaped particles. Satellite retrievals over bright desert surfaces are challenging owing to the lack of spectral contrast between the dust and the underlying surface. However, new techniques have been developed which are shown to be in relatively good agreement with AERONET estimates of AOD and with each other. This encouraging result enables relatively robust validation of numerical models which treat the production, transport, and deposition of mineral dust. The dust models themselves are able to represent large-scale synoptically driven dust events to a reasonable degree, but some deficiencies remain both in the Sahara and over the Sahelian region, where cold pool outflow from convective cells associated with the intertropical convergence zone can lead to significant dust production.

Distribution and availability of trace elements in municipal solid waste composts

Trace element contamination is one of the main problems linked to the quality of compost, especially when it is produced from urban wastes, which can lead to high levels of some potentially toxic elements such as Cu, Pb or Zn. In this work, the distribution and bioavailability of five elements (Cu, Zn, Pb, Cr and Ni) were studied in five Spanish composts obtained from different feedstocks (municipal solid waste, garden trimmings, sewage sludge and mixed manure). The five composts showed high total concentrations of these elements, which in some cases limited their commercialization due to legal imperatives. First, a physical fractionation of the composts was performed, and the five elements were determined in each size fraction. Their availability was assessed by several methods of extraction (water, CaCl2–DTPA, the PBET extract, the TCLP extract, and sodium pyrophosphate), and their chemical distribution was assessed using the BCR sequential extraction procedure. The results showed that the finer fractions were enriched with the elements studied, and that Cu, Pb and Zn were the most potentially problematic ones, due to both their high total concentrations and availability. The partition into the BCR fractions was different for each element, but the differences between composts were scarce. Pb was evenly distributed among the four fractions defined in the BCR (soluble, oxidizable, reducible and residual); Cu was mainly found in the oxidizable fraction, linked to organic matter, and Zn was mainly associated to the reducible fraction (iron oxides), while Ni and Cr were mainly present almost exclusively in the residual fraction. It was not possible to establish a univocal relation between trace elements availability and their BCR fractionation. Given the differences existing for the availability and distribution of these elements, which not always were related to their total concentrations, we think that legal limits should consider availability, in order to achieve a more realistic assessment of the risks linked to compost use.

Sensitivity of direct radiative forcing by mineral dust to particle characteristics

Airborne dust affects the Earth's energy balance — an impact that is measured in terms of the implied change in net radiation (or radiative forcing, in W m-2) at the top of the atmosphere. There remains considerable uncertainty in the magnitude and sign of direct forcing by airborne dust under current climate. Much of this uncertainty stems from simplified assumptions about mineral dust-particle size, composition and shape, which are applied in remote sensing retrievals of dust characteristics and dust-cycle models. Improved estimates of direct radiative forcing by dust will require improved characterization of the spatial variability in particle characteristics to provide reliable information dust optical properties. This includes constraints on: (1) particle-size distribution, including discrimination of particle subpopulations and quantification of the amount of dust in the sub-10 µm to <0.1 µm mass fraction; (2) particle composition, specifically the abundance of iron oxides, and whether particles consist of single or multi-mineral grains; (3) particle shape, including degree of sphericity and surface roughness, as a function of size and mineralogy; and (4) the degree to which dust particles are aggregated together. The use of techniques that measure the size, composition and shape of individual particles will provide a better basis for optical modelling.

Post-collisional lamprophyric event in Sierra Norte, Cordoba, Argentina: Mineralogical, geochemical and isotopic characteristics

Over 20 lamprophyre dykes, varying in width between a few centimeters and several meters, have been identified in central Sierra Norte - Eastern Pampean Ranges, Cordoba, Argentina. Their mineralogy and chemistry indicate that they are part of the calc-alkaline lamprophyres clan (CAL). They contain phenocrysts of magnesiohomblende +/- augite set in a groundmass of magnesiohornblende, calcic-plagioclase, alkali feldspar, and opaque minerals, which designate them as spessartite-type lamprophyres. Alteration products include chlorite, calcite and iron oxides after malfic phenocrysts, though some are partially replaced by actinolite. Feldspars are replaced by carbonate and clay minerals. The dykes are relatively primitive, and show restricted major element variation (SiO(2) 51.1-55.3 wt.%, Al(2)O(3) 12-16.6 wt.%, total alkalies 1.5-4.7 wt.%), high Mg# (55-77), high Cr contents (27-988 ppm) and moderate to high Ni contents (60-190 ppm). Lamprophyre LILE (e.g. Rb averages 110 ppm, Sr 211-387 ppm, Ba 203-452 ppm) are high relative to HFSE (e.g., Ta 0.2-1.6 ppm, Nb 4-11 ppm, Y 17-21 ppm), and are enriched in LREE (30-70 times chondrite). They are characterized by relatively high (208)Pb/(204)Pb (38.8-39.9), (207)Pb/(204)Pb(similar to 15.7), and (206)Pb/(204)Pb (18.7-20.1), combined with low (epsilon)epsilon(Nd) (-4.69 to -1.52) and a relative moderately high ((87)Sr/(86)Sr)(i) of 0.7055-0.7074. The Rb-Sr whole rock isochron indicates an Early Ordovician age of 485 +/- 25 Ma. The calculated T(DM) (1.7 Ga) suggests that these rocks appear to have originated from a reservoir that was created during a mantle metasomatism event related to the Pampean orogeny. The Sierra Norte lamprophyres show affinities with a subduction-related magma in an active continental margin. Their geochemical and isotopic features suggest a multicomponent source, composed of enriched mantle material variably contaminated by crustal components. The lamprophyric suite emplacement occurred at the dawning stage of the Pampean orogeny, in a regional post-collisional extensional setting developed in the Sierra Norte-Ambargasta batholith (SNAB) in Early Ordovician times. (C) 2008 Published by Elsevier Ltd.

Evidence of redox interactions between polypyrrole and Fe(3)O(4) in polypyrrole-Fe(3)O(4) composite films

The electrical properties of conducting polymers make them useful materials in a wide number of technological applications. In the last decade, an important effect on the properties of the conducting polymer when iron oxides particles are incorporated into the conductive matrix was shown. In the present study, films of polypyrrole were synthesized in the presence of magnetite particles. The effect of the magnetite particles on the structure of the polymer matrix was determined using Raman spectroscopy. Mass variations at different concentrations of Fe(3)O(4) incorporated into the conducting matrix were also measured by means of quartz crystal microbalance. Additionally, the changes in the resistance of the films were evaluated over time by electrochemical impedance spectroscopy in solid state. These results show that the magnetite incorporation decreases polymeric film resistance and Raman experiments have evidenced that the incorporation of magnetite into polymeric matrix not only stabilizes the polaronic form of the polypyrrole, but also preserves the polymer from further oxidation. (C) 2009 Elsevier Ltd. All rights reserved.

An investigation of the activation process of high temperature shift catalyst

The aim of this work is to address the activation process of a high temperature shift (HTS) catalyst, composed of Fe2O3/Cr2O3/CuO, by analyzing it before activation (HTS-V) and after activation (HTS-A) using complementary characterization techniques. The textural and morphological characterizations were done by transmission electron rnicroscopy (TEM) and nitrogen physisorption at 77 K; crystallographic structure was confirmed by X-ray diffraction (XRD); electronic structure was analyzed by X-ray absorption spectroscopy (XAS) and the chemical composition of the catalyst`s surface was obtained by X-ray photoelectron spectroscopy (XPS). The investigation pointed out that the HTS-V catalyst presents good textural and morphological properties, which are not deeply affected by the activation process (sample HTS-A). The iron oxide phase in the HTS-V catalyst is hematite whereas in HTS-A catalyst is magnetite with Fe2+/Fe3+ ratio close to the expected value (0.5). For both samples, the Cr ions seem to be incorporated in the iron oxide lattice with higher concentration at particle surface. In the HTS-V catalyst, the Cu ions have oxidation number II and occupy in average distorted octahedral sites; after the activation, the Cu ions are partially reduced, suggesting that the reduction of the Cu species is complex. (C) 2007 Elsevier B.V. All rights reserved.

Síntese de pigmentos cerâmicos inorgânicos nanométricos e encapsulados com estrutura core-shell pela rota dos precursores poliméricos

The present work has as objective the development of ceramic pigments based in iron oxides and cobalt through the polymeric precursor method, as well as study their characteristics and properties using methods of physical, chemical, morphological and optical characterizations.In this work was used iron nitrate, and cobalt citrate as precursor and nanometer silica as a matrix. The synthesis was based on dissolving the citric acid as complexing agent, addition of metal oxides, such as chromophores ions and polymerization with ethylene glycol. The powder obtained has undergone pre-ignition, breakdown and thermal treatments at different calcination temperatures (700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C). Thermogravimetric analyzes were performed (BT) and Differential Thermal Analysis (DTA), in order to evaluate the term decomposition of samples, beyond characterization by techniques such as BET, which classified as microporous materials samples calcined at 700 ° C, 800 º C and 900 º C and non-porous when annealed at 1000 ° C and 1100 º C, X-ray diffraction (XRD), which identified the formation of two crystalline phases, the Cobalt Ferrite (CoFe2O4) and Cristobalite (SiO2), Scanning Electron Microscopy (SEM) revealed the formation of agglomerates of particles slightly rounded;and Analysis of Colorimetry, temperature of 700 °C, 800 °C and 900 °C showed a brown color and 1000 °C and 1100 °C violet

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

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Relações solo-paisagem em uma litosseqüência arenito-basalto na região de Pereira Barreto, SP

Os objetivos deste trabalho foram estudar as relações solo-paisagem em uma litosseqüência de transição arenito-basalto e verificar a similaridade dos limites de superfícies geomórficas mapeados no campo com os limites mapeados a partir de técnicas geoestatísticas. Foi realizado o mapeamento de uma área de 530 ha, utilizando-se equipamento de GPS, e em seguida elaborou-se o Modelo de Elevação Digital, que possibilitou o estabelecimento da transeção de 2.100 m a partir do topo. Ao longo da transeção, o terreno foi estaqueado a intervalos regulares de 50 m, nos quais foram realizadas medidas da altitude para confecção do perfil altimétrico. As superfícies geomórficas foram identificadas e delimitadas conforme critérios topográficos e estratigráficos, com base em intensas investigações de campo. Coletaram-se amostras de solo em pontos laterais em 67 locais, nas superfícies geomórficas identificadas, nas profundidades de 0,0-0,25 m e 0,80-1,00 m. Além disso, foram abertas trincheiras nos segmentos de vertente inseridos nas superfícies geomórficas mapeadas. As amostras coletadas foram analisadas quanto a densidade do solo, textura, Ca2+, K+, Mg2+, SB, CTC, V, pH (água e KCl), SiO2, Al2O3 e Fe2O3 (ataque por H2SO4), óxidos de Fe livres extraído com ditionito-citrato-bicarbonato e ferro mal cristalizado extraídos com oxalato de amônio. A fração argila desferrificada foi analisada por difração de raios X. A compartimentação da paisagem em superfícies geomórficas e a identificação do material de origem mostraram-se bastante eficientes para entendimento da variação dos atributos do solo. A análise individual desses atributos por meio de estatística univariada auxiliou na discriminação das três superfícies geomórficas. O uso de técnicas de geoestatística permitiu a confirmação de que mesmo os atributos do solo apresentaram limites próximos aos das superfícies geomórficas.