The oil from the macaúba (Acrocomia aculeata) fruit, a native palm in Brazil, has a real potential for the industrial production of biodiesel. This report describes an experimental work devoted to monitor the chemical behavior of the fatty acid methyl esters from oil of the macaúba fruit kernel and the leaching of metal elements into the biodiesel put in contact with the ASTM A283 grade C and API X65 carbon steels, used to build fuel storage tanks and biodiesel pipelines. The mean values of esters contents points that the analytical precision from atomic absorption measurements was not enough to support a statistically reliable interpretation of the chemical leaching of metals into the biodiesel; a more accurate set of data must be obtained with more sensitive chemical analytical techniques. From the Mössbauer data, the surface of the non - galvanized steels in contact with this biodiesel for up to 105 days tend to be somehow protected against most oxidative reactions even in direct contact with air, although few amount magnetite (Fe3O4) was detected.

The production of methyl esters via transesterification reaction of triacylglycerides of macaúba and palm kernel oils, with subsequent atmospheric distillation and separation of six fractions of the produced biodiesel, corresponding to 60% of its initial volume, is reported. The composition in esters of the produced biodiesel, its fractions and remaining residue of the distillation was determined by gas chromatography. This analytical procedure has allowed to monitor the content in esters for each distilled fraction. The fractions richer in C8:0, C10:0, C12:0, C14:0 is intended to be used as an aviation fuel, in blends with the Jet-A1 biokerosene. The residues from the distillation with higher molecular weights than those corresponding to esters C16:0, C18:0 and C18:1 are destined to other combustion engines as any conventional biodiesel. For the biodiesel obtained from the macaúba kernel, this distillation led to an enrichment from 45.86% to up to 74.35% in the C12:0 ester. For the palm kernel biodiesel, the corresponding enrichment was from 66.76% up to 82.96%. Through this simple distillation, it was thus possible to effectively enrich, in C8:0 to C14:0 esters, the initial crude biofuel, with an efficiency of 30% for the macaúba and 11.5% for the palmiste biodiesel.

Abstract: Chilean soils derived from volcanic ashes are a natural source of iron oxides. Due to their properties, mineralogy, and surface characteristics, iron oxides from Chilean soils are potential candidates for technological applications such as heterogeneous catalysis. However, before a direct application in catalysis, pre-treatment methods are necessary to concentrate iron oxides from bulk volcanic soils. Here, we provide a comprehensive review of pre-treatment strategies for iron oxide concentration including physical separation and selective chemical dissolutive methods for application in catalytic processes, such as the water gas shift (WGS) and Fenton reactions. For preparation of WGS catalyst from volcanic soils, thermal treatment has been demonstrated to be effective, yielding enhanced results for Andisols compared to Ultisols. Based on mineralogical characterisation, it seems that WGS reaction efficiency depends on mineralogical phase shift and the changes of Fe2+/Fe3+ ratio, produced through heating. In addition, Ultisols have shown as efficient catalysts in Fenton and Fenton-like processes, after application of physical and chemical pre-treatments to different size-fractions of the soil sample, improving the yield performance of catalysts. Magnetic separates from the Ultisol sand fraction (compared to the silt+clay fractions) demonstrate the best catalytic performance as Fenton reagent due to their natural magnetite and titanomagnetite content. Application of NaOH selective dissolutive treatment to silt+clay fraction of volcanic soils also produces Fenton and Fenton-like catalyst with improved performance. Our review indicates that catalytic performance can be explained not only by the iron oxide mineral content but also by their characteristics and magnetic properties. The application of the appropriate physical and chemical pre-treatment methods can modulate and enhance the catalytic capabilities of iron oxides from volcanic soils.

ABSTRACT In the Southern Espinhaço Mountain Chain and in the Upper Jequitinhonha Valley, magnetic soils, in different pedogenetic stages, are found to be forming over intrusions of basic lithology. The essential chemical and mineralogical properties of samples from magnetic soil profiles from those two physiographic environments in the state of Minas Gerais, Brazil, are reported. Three of the pedons (Rhodic Kandiustox – RKox, Rhodic Haplustox – RHox, and Typic Argiustoll - TAoll) were identified as being indeed developed over basic rocks; the fourth pedon (Typic Haplustox - THox) is currently forming on an acidic rock. Particle size and routine chemical analyses were performed on samples from all horizons of the four selected soil profiles. For a deeper insight into the dominant mineralogy of each diagnostic soil horizon, the elemental contents, expressed in terms of the corresponding metal cation oxides, namely Fe2O3, Al2O3, and MnO2, were obtained from digesting the whole soil samples with sulfuric acid. A similar chemical analytical procedure was performed for the residual solid extracts obtained from attacking the whole soil materials with mixtures of (i) dithionite - citrate - bicarbonate and (ii) oxalate - oxalic acid. The soil samples were also analyzed by Mössbauer spectroscopy at room temperature (~298 °K) in an attempt to better identify the main magnetic iron oxides. Maghemite (δFe2O3) was found in all samples and magnetite (Fe3O4) was identified only for the sample from the Typic Argiustoll. The pedogenetic loss of silica and consequent accumulation of iron and aluminum oxides along the profile are found to be somehow correlated to the weathering sequence in the soils forming on basic rocks: TAoll < RKox < RHox.

Localizado na porção centro-oeste do Estado de Minas Gerais, o Quadrilátero Ferrífero abrange uma área de aproximadamente 7.000 km². Desde o século XVII, a região é conhecida como uma província aurífera e ferrífera, sendo por essa razão uma das regiões mais bem estudadas do Brasil no contexto geológico. A região é de topografia muito acidentada, onde predominam solos pouco evoluídos pedogeneticamente, com destaque para Cambissolos Háplicos, Neossolos Litólicos e Neossolos Regolíticos. Em menor proporção e em rampas de colúvio (relevo suave ondulado), ocorrem Latossolos Vermelhos muito ricos em Fe, anteriormente denominados Latossolos Ferríferos. Neste trabalho, foram realizados estudos para caracterizar física, química e mineralogicamente amostras de nove perfis de Latossolos Vermelhos férricos e perférricos, desenvolvidos de itabirito e rochas afins no Quadrilátero Ferrífero, com os objetivos de melhor entender sua gênese e avaliar critérios taxonômicos que permitam sua diferenciação no SiBCS, em níveis categóricos mais baixos. Os elevados valores de densidade de partículas são peculiares nesses solos e, ao lado da estrutura forte, muito pequena e granular, são fatores que contribuem para subestimar os teores de argila e superestimar os de silte, resultando em relação silte/argila maior do que aquela proposta pelo SiBCS para os Latossolos. A variação dos teores de SiO2, Fe2O3, Al2O3, TiO2, MnO, P2O5 e de alguns elementos-traço aponta para a diversidade na composição química do itabirito ou, ainda, provável mistura com rochas filíticas da região. Os valores das relações Fe2O3/TiO2 (não molecular) e TiO2/Fe2O3 (molecular) revelaram-se diferentes daqueles sugeridos na literatura para separação de Latossolos Vermelhos desenvolvidos de itabirito daqueles de rochas máficas. As frações areia, silte e argila apresentaram grande variação na atração magnética, com as duas primeiras frações evidenciando maior magnetização, em razão da presença de magnetita. Os valores de substituição isomórfica de Fe por Al variaram 0,07 a 0,11 e 0,09 a 0,38 mol mol-1 nas estruturas da hematita e magnetita, respectivamente.

Located in the Midwest of the State of Minas Gerais, a region called Quadrilátero Ferrífero covers an area of approximately 7,000 km². Since the seventeenth century, it is known as gold- and iron-producing province, and the geological context is therefore one of the best-studied of Brazil. The regional topography is very rugged, with mostly poorly developed pedogenesis, especially Cambissolos Háplicos, Neossolos Litólicos and Neossolos Regolíticos. In a smaller proportion and on colluvial ramps (hilly relief), very Fe-rich Latossolos Vermelhos occur, formerly Latossolos Ferríferos. This study characterized the physical, chemical and mineralogical properties of samples from nine ferric and hyperferric Latossolo Vermelho profiles, developed from itabirite and related rocks in the Quadrilátero Ferrífero, with the objectives of improving the understanding of their genesis and establish taxonomic criteria for their differentiation in the SiBCS at lower categorical levels. The high particle density values in these soils are peculiar and along with the strong, very small and granular structure, are factors that contribute to underestimate clay and overestimate silt, resulting in a higher silt/clay ratio than proposed by SiBCS for Latossolos. Variations in the levels of SiO2, Fe2O3, Al2O3, TiO2, MnO, P2O5, and of some trace elements indicate the diversity in the chemical composition of itabirite or a probable mixture with phyllitic rocks of the region. The ratios of Fe2O3/TiO2 (non-molecular) and TiO2/Fe2O3 (molecular) reported in the literature for separation of Latossolos Vermelhos differed between soils developed from itabirite and from mafic rocks. The magnetic attraction in sand, silt and clay varied greatly; due to the presence of magnetite, magnetization was higher in the former two fractions. The values of isomorphic Al-for-Fe substitution ranged from 0.07 to 0.11 and from 0.09 to 0.38 mol mol-1 in the structures of hematite and magnetite, respectively.

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.

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.

In this work, controlled reduction of perovskites supported on Al2O3 was used to prepare thermally stable nanodispersed iron catalysts based on Fe0/La2O3/Al2O3. The perovskites composites LaFe0.90Mn0.08Mo0.02O3(25, 33 and 50 wt (%)) /Al2O3 and LaFe0.90Mn0.1O3(25 wt (%)) /Al2O3 were prepared and characterized by XRD, BET, TPR, SEM and Mössbauer spectroscopy. XRD for unsupported perovskite showed the formation of a single phase perovskite structure. The Mössbauer spectra of the perovskites were fitted with hyperfine field distribution model for the perovskite. Supported perovskites on Al2O3 showed a decrease of the hyperfine field in respect to unsupported perovskite, due to decrease of particle size and dispersion of the Fe3+ specimens on the support. Also showed broaden lines and relaxation effects due to the small particle size. To produce the Fe0 catalyst, the composite perovskite(25%)/Al2O3 was reduced with H2 at 900, 1000 and 1100 °C for 1 hour. XRD data indicated the formation of Fe0 catalyst with particles sizes of ca. 35 nm. The Mössbauer spectrum showed the formation of metallic iron and doublets corresponding to species of octahedric Fe2+ and Fe3+ sites dispersed on Al2O3. These catalysts showed improved stability towards sintering even upon treatment at 1000 and 1100 °C under H2.

Chemical reactions in the solid state are often not included in undergraduate chemistry curricula, due to requirements for special laboratory facilities such as ovens and precision weighing balances. This work aims to describe novel and relatively simple magnetite chemical syntheses in dry medium, which could also be used as an alternative for freshmen chemistry experiments. The proposed reaction was carried out in a muffle furnace by heating (i) a sol-gel preparation and (ii) natural hematite, under nitrogen atmosphere at 400 ºC. The synthesized magnetite was characterized with powder X-ray diffraction and Mössbauer spectroscopy. Results show that magnetite samples have chemical properties as well as crystalline structure quite similar to those of standard natural magnetite.

This work presents a chemical study of human bones painted red located at the Morro dos Ossos site, Piauí State, Brazil. The pigment was studied using X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), complexation reactions with thiocyanate and UV-Vis absorption spectroscopy. The results confirmed the presence of ochre and that the pigment layer is essentially composed of a mixture of clay and hematite, α-Fe2O3.

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.

O beneficiamento industrial do caulim envolve a remoção de óxidos e hidróxidos de ferro e outras impurezas, que conferem coloração indesejável ao produto final e depreciam seu valor comercial, particularmente se destinado à indústria de papel. A lixiviação química, na linha de processamento industrial, pode ser feita com tratamentos com hipossulfito de sódio, zinco metálico e ácidos sulfúrico e fosfórico, para redução, solubilização e remoção de compostos ferruginosos. A fim de minimizar o impacto ambiental, o efluente ácido, procedente da etapa de lixiviação, deve ser inicialmente neutralizado, usualmente por óxido de cálcio. O resíduo sólido resultante contém fósforo, zinco e cálcio, entre outros nutrientes, o que sugere seu uso como fonte de macro e micronutrientes. O principal objetivo do presente estudo foi avaliar o uso do resíduo sólido como fertilizante agrícola, em experimentos de incubação em casa de vegetação, em amostras de dois solos: um de textura média e outro argiloso. A pequena alteração do pH do solo, em função da aplicação do resíduo, não constitui fator limitante à sua aplicação na agricultura. A evolução das concentrações de cálcio trocável, e fósforo e zinco extraíveis por Mehlich-1, em função do tempo de incubação, confirmam a potencialidade de uso do resíduo industrial como fertilizante agrícola.

The industrial refining of kaolin involves the removal of iron oxides and hydroxides along with other impurities that cause discoloration of the final product and depreciate its commercial value, particularly undesirable if destined to the paper industry. The chemical leaching in the industrial processing requires treatments with sodium hyposulfite, metallic zinc, or sulfuric and phosphoric acids, in order to reduce, dissolve and remove ferruginous compounds. To mitigate the environmental impact, the acidic effluent from the leaching process must be neutralized, usually with calcium oxide. The resulting solid residue contains phosphorous, zinc, and calcium, among other essential nutrients for plant growth, suggesting its use as a macro and micronutrient source. Samples of such a solid industrial residue were used here to evaluate their potential as soil fertilizer in an incubation greenhouse experiment with two soil samples (clayey and medium-textured). The small pH shift generated by applying the residue to the soil was not a limiting factor for its use in agriculture. The evolution of the concentrations of exchangeable calcium, and phosphorous and zinc extractability by Mehlich-1 extractant during the incubation period confirms the potential use of this industrial residue as agricultural fertilizer.

O objetivo deste trabalho foi efetuar a caracterização mineralógica dos óxidos de ferro de horizontes B de três perfis de solos desenvolvidos sobre gnaisse do geodomínio do Complexo Bação, no Quadrilátero Ferrífero, em Minas Gerais. As amostras foram coletadas ao longo dos segmentos de alta, média e baixa vertente. As frações de terra fina (diâmetro médio, fi = 2 mm) foram separadas, em todas as amostras. A composição química dos elementos maiores foi determinada por meio da técnica de fluorescência de raios X; a análise mineralógica foi realizada com difratometria de raios X e espectroscopia Mössbauer. Todas as amostras têm composição mineralógica similar, cuja ocorrência geral corresponde à seqüência quartzo >> gibbsita > caulinita > goethita. Os resultados Mössbauer a 4,2 K confirmam a coexistência de goethita (majoritária) e hematita. Os conteúdos de alumínio isomórfico foram deduzidos dos valores de campos hiperfinos e correspondem às seguintes fórmulas químicas das goethitas: alfaFe0,79Al0,21OOH (alta vertente), alfaFe0,75Al0,25OOH (meia vertente) e alfaFe0,78Al0,22OOH (baixa vertente). A dinâmica de transformação dos óxidos de ferro nos horizontes B ao longo da vertente é um indicador das oscilações paleoclimáticas na área: goethita mais aluminosa é um indicador do paleoambiente úmido, e goethita menos aluminosa revela condições pedogênicas mais secas.

The objective of this work was to characterize iron oxides from B-horizons of three soil profiles developing on gneiss of the Bação Complex geodomain in the Quadrilátero Ferrífero, Minas Gerais, Brazil. Samples were collected from the uppest, middle and lowest segments along the slope. The earth fine fractions (mean diameter, phi = 2 mm) were separated for all samples. The chemical composition of the major elements was determined with the X-ray fluorescence technique; the mineralogical analysis was performed with powder X-ray diffractomer and Mössbauer spectroscopy. All samples have similar mineralogical composition, with a general occurrence corresponding to the sequence quartz >> gibbsite > kaolinite > goethite. From the 4.2 K-Mössbauer results, the coexistence of goethite (major) and hematite is confirmed. The isomorphic aluminum contents, as they were deduced from the hyperfine fields, lead to the following chemical formulas for goethites: alphaFe0.79Al0.21OOH (upslope), alphaFe0.75Al0.25OOH (midslope) and alphaFe0.78Al0.22OOH (downslope). The iron oxides transformation dynamics in B horizons along the slope is a useful indicator of the paleo-climatic oscillations in this area: aluminous goethite is an indicator of humid paleo-environments, whereas aluminous-poorer goethite reveals drier pedogenic conditions.

Solos magnéticos derivados de tufito da região do Alto Paranaíba (MG) têm mineralogia bastante variável, mas são relativamente ricos em óxidos de Fe isoestruturais ao espinélio, mais especificamente: (Ti, Mg)-magnetita e (Ti, Mg)-maghemita. No presente trabalho, foram estudados os concentrados magnéticos (magnetização de saturação, 34,4 < sigma/J T-1 kg-1 < 43,7) da fração areia de pedomateriais de um Brunizém (Chernossolo) (amostras AP31CR; AP31B e AP31A) e de um Chernossolo Léptico (AP33CR e AP33A) derivados de tufito, coletados no município de Patos de Minas (MG). Foram identificadas, por difratometria de raios X (método do pó) e espectroscopia Mössbauer do 57Fe, a 298 K e a 110 K, maghemita (gamaFe2O3) e hematita (alfaFe2O3) e uma inédita magnesioferrita (fórmula ideal, MgFe2O4), inédita em solos do Brasil, nas frações minerais desses materiais magnéticos. Observou-se, também, que as proporções ponderais e os tamanhos de partículas dos óxidos de Fe variam progressivamente ao longo dos perfis estudados. Os diâmetros médios estimados dos cristalitos de magnesioferrita variam progressivamente, em cada perfil: 27 nm (concentrado magnético da amostra AP31CR); 25 nm (AP31B); 23 nm (AP31A); 48 nm (AP33CR) e 32 nm (AP33A). A proporção de Al isomorficamente substituinte na hematita aumenta sistematicamente de 5 a 13 mol %, da base para o topo do perfil AP31, e tende a se manter constante, em torno de 9 mol %, no perfil AP33. Propõe-se um modelo geral de transformação envolvendo somente óxidos de Fe, em que magnesioferrita é o precursor pedogenético da maghemita, até hematita, nesses pedossistemas: MgFe2O4 -> gFe2O3 -> aFe2O3.

Tuffite-derived magnetic soils in the Alto Paranaíba region, State of Minas Gerais, Brazil, have a variable mineralogy and are assumed to contain iron oxides that are isoestructural to spinel, more specifically, (Mg,Ti)-rich magnetite and maghemite. In this study, magnetic portions (saturation magnetization, 34.4 < sigma/J T-1 kg-1 < 43.7) were separated from sand fractions of pedomaterials of a Brunizem (Chernosol) (samples labeled AP31CR; AP31B and AP31A) and of a leptic Chernosol (AP33CR e AP33A) developed from tuffite were collected near the city of Patos de Minas, MG. Maghemite (gammaFe2O3), hematite (alphaFe2O3) and a reportedly identified magnesioferrite (ideal formula, MgFe2O4) were found to also occur in these magnetic extracts, as it could be deduced from X ray diffractometry and 298 K and 110 K 57Fe Mössbauer spectroscopy data. It was also observed that the relative proportions and particle sizes of the iron oxides vary progressively in each soil profile. Mean crystallite diameters are 27 nm (magnetic portion of sample AP31CR); 25 nm (AP31B); 23 nm (AP31A); 48 nm (AP33CR) and 32 nm (AP33A). The isomorphical Al contents in hematite also increase systematically from 5 to 13 mol%, from the bottom to the top of the AP31 profile and tend to be constant at about 9 mol% along the AP33 profile. An overall model was proposed including the main transformation pathway involving only iron oxides, in which magnesioferrite is the pedogenetic precursor of maghemite up to hematite in these pedosystems: MgFe2O4 -> gFe2O3 -> aFe2O3.

Sand samples collected from two sampling sites on Guarapari and Iriri beaches, state of Espírito Santo, Brazil, were studied in an attempt to better describe their chemical and mineralogical compositions and radioactive behaviors. The sands were found to contain about 6 (Guarapari) and 2 dag kg-1 (Iriri) of rare earth and thorium that, if allocated to the monazite-(Ce) structure, lead to the averaged formulae Ce3+0,494Gd3+0,012La3+0,209Nd3+0,177Pr3+0,040Sm3+0,024Th4+0,033 (PO4) and Ce3+0,474La3+0,227Nd3+0,190Pr3+0,044Sm3+0,032Th4+0,024 (PO4). From Mössbauer spectroscopy data, the magnetic fractions of these sands were found to contain stoichiometric hematite (47.4 dag kg-1, from Guarapari, and 25.1 dag kg-1, from Iriri) and magnetite (44.1 and 58.8 dag kg-1). The specific alpha and beta radiation activities were also measured for both samples.