Nióbia magnética como adsorvente de contaminantes orgânicos em meio aquoso: efeito da temperatura e do pH

This work describes novel materials based on pure iron oxide and iron oxide/niobia composite to produce a magnetic adsorbent. These materials were prepared with synthetic iron oxide and characterized by powder XRD, SEM, FTIR, TPR and Mössbauer spectroscopy. Results showed that the main iron oxides formed were goethite (aFeOOH) and maghemite (gFe2O3) with small particle size. The iron oxide and iron oxide/niobia composite showed high adsorption ability for organic compounds. The positive enthalpy indicated an endothermic adsorption process suggesting physical adsorption.

Estudo sobre a utilização da lama vermelha para a remoção de corantes em efluentes têxteis

Red mud is the principal residue of the alumina (Al2O3) industry. Generated during the Bayer process, it is characterized by strong alkalinity and ion exchange. Iron oxides are the principal component (30 to 60%). Annually millions of tons of red mud are generated in the world. Red mud disposal is responsible for a large part of the cost of alumina production. On the other hand, textile industry wastewaters containing dyes have a great impact on the environment and on human health. In this paper the possibility of applying red mud for the removal of dyes was investigated by two processes: adsorption and degradation by the Fenton reagent.

Espectroscopia Mössbauer na caracterização de compostos ferrosos em solos e sua relação com retenção de fósforo

The chemical role of iron-bearing compounds on the dynamics of phosphorus in selected Brazilian latosols was investigated. The iron oxides were characterized in an attempt to assess their main chemical-mineralogical properties influencing the ion sorption mechanisms in those pedosystems. It was found that increasing total iron contents tend to increase the phosphorus adsorption capacity in the selected soils. 110 K-Mössbauer data reveal that the dominant iron oxides are hematite and goethite. Particularly for the yellower soil samples some prominent doublets, more certainly due to superparamagnetic relaxation, may be assigned to corresponding fractions of relatively small-sized particles.

Mecanismos químicos e mineralógicos de transformação da magnesioferrita de solo derivado de tufito, da região do Alto Paranaíba, MG

Magnetic soils forming on tuffite of the region of Alto Paranaíba, Minas Gerais, Brazil, usually contain iron-rich spinels exceptionally rich in magnesium and titanium. In this work, samples of the magnetically separated portion from the sand fraction of a Brunizém (Chernossolo) and from its mother-rock material were analyzed with synchrotron X-ray diffraction and 57Fe-Mössbauer spectroscopy. Magnesioferite (MgFe2O4) and maghemite (its pure non-stoichiometric spinel structure, Fe8/3 ⊕ 1/3 O4, where ⊕ = cation vacancy, corresponds to γFe2O3) were the magnetic iron oxides so identified. Basing on these data, a consistent chemical-mineralogical model is proposed for the main transformation steps involving these iron oxides in the pedosystem, starting on magnesioferrite to finally render hematite (αFe2O3), passing through maghemite as an intermediate specie.

pH effect on the synthesis of magnetite nanoparticles by the chemical reduction-precipitation method

This work aimed at putting in evidence the influence of the pH on the chemical nature and properties of the synthesized magnetic nanocomposites. Saturation magnetization measurements evidenced a marked difference of the magnetic behavior of samples, depending on the final pH of the solution after reaction. Magnetite and maghemite in different proportions were the main magnetic iron oxides actually identified. Synthesis with final pH between 9.7-10.6 produced nearly pure magnetite with little or no other associated iron oxide. Under other synthetic conditions, goethite also appears in proportions that depended upon the pH of the synthesis medium.

Pigmentos de pinturas rupestres pré-históricas do sítio Letreiro do Quinto, Pedro II, Piauí, Brasil

The Letreiro do Quinto rock shelter is located in the rural area of the city of Pedro II, Piauí, Brazil. The sandstone walls of the shelter are covered with prehistoric rupestrian paintings, painted in patterns of yellow and light and dark red hues. The chemical-mineralogical characterization of the prehistoric pigments was made with energy dispersive spectroscopy, scanning electron microscopy, energy dispersive X-ray fluorescence and 57Fe transmission Mössbauer spectroscopy at 110 K. Results confirm the occurrence of hematite- and goethite-rich ochres and also that the pigment layers are indeed made of a mixture of clay minerals mixed with iron oxides.

Óxidos de ferro e suas aplicações em processos catalíticos: uma revisão

A review of most of the reported studies on the use of iron oxides as catalyst in specific processes, namely Haber-Bosch reaction, Fischer-Tropsch synthesis, Fenton oxidation and photolytic molecular splitting of water to produce gaseous hydrogen, was carried out. An essential overview is thus presented, intending to address the fundamental meaning, as well as the corresponding chemical mechanisms, and perspectives on new technological potentialities of natural and synthetic iron oxides, more specifically hematite (α-Fe2O3), goethite (α-FeOOH), magnetite (Fe3O4) and maghemite (γ-Fe2O3), in heterogeneous catalysis.

Conversão química de no e co sobre catalisadores à base de óxidos de cobalto ou de ferro

Cobalt or iron oxides supported or not on zeolite Hbeta were prepared and evaluated in the reduction reaction of NO by CO in presence of O2, SO2 or H2O. XRD results evidenced the Hbeta structure and the formation of Co3O4 and Fe2O3. TPR-H2 analysis showed complete reduction of cobalt oxide at lower temperatures than for iron oxide. The catalysts are quite active and the activity depends on the reaction temperature. The highest conversions rates were observed for pure iron oxide, which can be a relatively low cost catalyst for reduction of NO by CO, with high selectivity towards the N2 formation.

VIS-NIR SPECTROMETRY, SOIL PHOSPHATE EXTRACTION METHODS AND INTERACTIONS OF SOIL ATTRIBUTES

The objective of this study was to evaluate the relationships between the spectra in the Vis-NIR range and the soil P concentrations obtained from the PM and Prem extraction methods as well as the effects of these relationships on the construction of models predicting P concentration in Oxisols. Soil samples' spectra and their PM and Prem extraction solutions were determined for the Vis-NIR region between 400 and 2500 nm. Mineralogy and/or organic matter content act as primary attributes allowing correlation of these soil phosphorus fractions with the spectra, mainly at wavelengths between 450-550, 900-1100 nm, near 1400 nm and between 2200-2300 nm. However, the regression models generated were not suitable for quantitative phosphate analysis. Solubilization of organic matter and reactions during the PM extraction process hindered correlations between the spectra and these P soil fractions. For Prem,, the presence of Ca in the extractant and preferential adsorption by gibbsite and iron oxides, particularly goethite, obscured correlations with the spectra.

APLICAÇÃO DE ÓXIDOS DE FERRO NANOESTRUTURADOS COMO ADSORVENTES E FOTOCATALISADORES NA REMOÇÃO DE POLUENTES DE ÁGUAS RESIDUAIS

New techniques for treating wastewater, particularly the removal or degradation of organic pollutants and heavy metals, among other pollutants, have been extensively studied. The use of nanostructured iron oxides as adsorbent and photocatalyst for the removal of these contaminants has proved a promising approach, not only because of their high treatment efficiency, but also for their cost-effectiveness, having the flexibility for in situ and ex situ applications. In this review, we briefly introduced the most used kinds of iron oxide nanoparticles, some synthesis techniques for iron oxide nanostructure formation, their potential benefits in environmental clean-up, and their recent advances and applications in wastewater treatment. These advances range from the direct applications of synthesized nanoparticles as adsorbents for removing toxic contaminants or as catalysts to oxidize and break down noxious contaminants (including bacteria and viruses) in wastewater, to integrating nanoparticles into conventional treatment technologies, such as composite photocatalytic filters (membranes, sand and ceramic) that combine separation technology with photocatalytic activity. Finally, the impact of nanoparticles on the environment and human health is briefly discussed.

Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

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.