The presence of organic matter and its effect on iron removal in ground water /

Vita.

Evaluation of residual iron in carbon nanotubes purified by acid treatments

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Profiles of iron concentration from GoFlow bottles during the CARUSO-EISENEX experiment

An in situ iron enrichment experiment was carried out in the Southern Ocean Polar Frontal Zone and fertilized a patch of water within an eddy of the Antarctic Circumpolar Current (EisenEx, Nov. 2000). During the experiment, a physical speciation technique was used for iron analysis in order to understand the changes in iron distribution and size-fractionations, including soluble Fe (<200 kDa), colloidal Fe (200 kDa-0.2 µm) and labile particle Fe (>0.2 µm), throughout the development of the phytoplankton bloom. Prior to the first infusion of iron, dissolved (<0.2 µm) iron concentrations in the ambient surface seawater were extremely low (0.06±0.015 nM) with colloidal iron being a minor fraction. For the iron addition, an acidified FeSO4 solution was released three times over a 23-day period to the eddy. High levels of dissolved iron concentrations (2.0±1.1 nM) were measured in the surface water until 4 days after the first iron infusion. After every iron infusion, when high iron concentrations were observed before storm events, there was a significant correlation between colloidal and dissolved iron concentrations ([Colloidal Fe]=0.7627[Dissolved Fe]+0.0519, R2=0.9346). These results indicate that a roughly constant proportion of colloidal vs. dissolved iron was observed after iron infusion (~76%). Storm events caused a significant decrease in iron concentrations (<0.61 nM in dissolved iron) and changed the proportions of the three iron size-fractions (soluble, colloidal and labile particle). The changes in each iron size-fraction indicate that colloidal iron was eliminated from surface mixed layer more easily than particulate and soluble fractions. Therefore, particle and soluble iron efficiently remain in the mixed layer, probably due to the presence of suspended particles and naturally dissolved organic ligands. Our data suggest that iron removal through colloidal aggregation during phytoplankton bloom should be considered in the oceanic iron cycle.

Hydrofluoric acid pre-treatment for improving 13C CPMAS NMR spectral quality of forest soils in south-east Queensland, Australia

Hydrofluoric acid (HF) was used to pre-treat forest soils of south-east Queensland for assessing the effectiveness of iron (Fe) removal, carbon (C) composition using C-13 cross-polarisation (CP) with magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) before and after the HF pre-treatment, and the improvement of C-13 CPMAS NMR spectra. Soil samples were collected from 4 experimental sites of different soil types, harvest residue management or prescribed burning, and tree species. More than 86% of Fe was in all soil types removed by the HF treatment. The C-13 NMR spectral quality was improved with increased resolution, especially in the alkyl C and O-alkyl C regions, and reduced NMR run-time (1-5 h per sample compared with >20 h per sample without the pre-treatment). The C composition appeared to alter slightly after the pre-treatment, but this might be largely due to improved spectrometer conditions and increased resolution leading to more accurate NMR spectral integration. Organic C recovery after HF pre-treatment varied with soil types and forest management, and soluble soil organic matter (SOM) could be lost during the pre-treatment. The Fourier Transform-Infrared (FT-IR) spectra of HF extracts indicated the preferential removal of carboxylic C groups during the pre-treatment, but this could also be due to adsorbed water on the mineral matter. The NMR spectra revealed some changes in C composition and quality due to residue management and decomposition. Overall, the HF treatment was a useful pre-treatment for obtaining semi-quantitative C-13 CPMAS NMR spectra of subtropical Australian forest soils.

Caracterização de águas do processo e optimização dos consumos de água nos vários circuitos da Petibol, S.A. – Embalagens de Plástico

A empresa Petibol, S.A. – Embalagens de plástico centra-se na produção de embalagens de plástico a partir da matéria-prima Poliestireno Expandido (EPS) e Polipropileno Expandido (EPP). A empresa possui uma preocupação ao nível da qualidade da água e do aproveitamento energético, tendo desta forma surgido a realização do estudo na unidade industrial, com o objectivo de anular e/ou diminuir as possíveis lacunas existentes na unidade industrial. Numa primeira etapa foi realizada uma caracterização global à qualidade da água e à empresa, actualizando-se os esquemas já existentes, contabilizando-se os custos actuais relativamente aos processos no circuito da água (arrefecimento, aquecimento e pressurização), e por fim, efectuou-se um levantamento in loco do circuito de água, relativamente à pressão, temperatura e caudal. Numa fase posterior, foram propostos equipamentos e processos, tendo em vista a colmatação dos problemas identificados, realizando-se um subsequente estudo relativamente aos custos inerentes a esses novos processos. A caracterização à água foi avaliada em diferentes pontos do circuito industrial, tendo-se determinado na Sala de Bombagem que o filtro de areia não possuía as dimensões mais apropriadas, existindo também um problema a nível mecânico associado ao processo de contra-lavagem. Tais factos podem ser a causa da ocorrência de um aumento do teor de sólidos após a passagem na camada filtrante. Relativamente ao amaciador, este deveria amaciar de forma completa a água para alimentação à caldeira, embora se tenha registado à saída do amaciador uma dureza de 21,3 mg/L, denunciando problemas na troca iónica. No que toca à água de alimentação à caldeira, verifica-se a existência de parâmetros que não se encontram de acordo com os critérios enunciados para uma óptima qualidade, sendo eles o pH (10,14), condutividade (363 μS/cm), teor de ferro (1,21 mg/L) e a dureza (16 mg/L). De salientar que somente o teor de cobre, que se encontra em quantidades vestigiais, apresenta-se de acordo com os valores impostos. No que respeita à água da caldeira, esta apresenta parâmetros incompatíveis com os recomendados, sendo eles a condutividade (7350 μS/cm), teor de sólidos dissolvidos (5248 mg/L) e alcalinidade total (780 mg/L). De referir que o valor de pH (11,8) não se encontra de acordo com a aplicação do tratamento “fosfato-pH coordenado”. Em relação aos parâmetros com valores que se encontram dentro dos limites, estes correspondem à dureza (0 mg/L), ao teor de fosfatos (45 mg/L) e teor de sílica (0 mg/L). A água do circuito de arrefecimento foi sujeita a uma análise microbiológica, que corroborou a presença de um biofilme. Um dos problemas enunciados pela empresa, prendia-se com a impossibilidade de descarga, no colector municipal, dos condensados dos compressores, visto apresentarem uma quantidade de óleo de cerca de 43,3 mg/L, equivalente a quatro vezes o valor limite de emissão, de acordo com a legislação municipal. Por fim, o efluente de descarga industrial apresenta um valor de pH (10,3) acima do intervalo permitido por lei (6,0 – 9,0), sendo que a corrente que mais contribui para este acréscimo de pH corresponde à corrente proveniente da água de purga, visto esta apresentar um valor de pH de 12,22. De maneira a contornar os parâmetros enunciados, é proposto a substituição do filtro de areia da Sala de Bombagem, assim como a inserção de um conjunto de medidas de remoção de ferro e desinfecção, sendo a conjugação de arejamento, coagulação, filtração e desinfecção, por parte do hipoclorito, a proposta apresentada. Aos condensados dos compressores é apresentado um sistema de separação, que possibilita a remoção do óleo da água, e uma consequente descarga da mesma. Actualmente, não existe qualquer filtro de areia no circuito de arrefecimento da água, sendo proposto assim esse equipamento, de forma a minorar o desenvolvimento da população microbiana, bem como a permitir uma maior eficiência na transferência de calor na torre de arrefecimento. Relativamente à descarga industrial, é recomendável a colocação de um sistema de regularização automática de pH. A inserção de uma válvula de três vias permite um aproveitamento energético e de água, a partir da confluência da água oriunda dos furos com a água do tanque de água fria, sendo posteriormente alimentada à central de vácuo. No estudo da recuperação energética, um outro equipamento avaliado correspondeu à serpentina, no entanto, verificou-se que a poupança no consumo de gás natural era de apenas 0,005%, o que não se mostrou uma proposta viável. O orçamento de todos os equipamentos é de 11.720,76 €, possibilitando não só um melhor funcionamento industrial, como um menor impacto a nível ambiental. Os custos futuros de funcionamento aumentam em 3,36%, tendo a pressurização um aumento do seu custo em 3,4% em relação ao custo actual, verificando-se um custo anual de 10.781,21€, em relação aos processos de arejamento, coagulação e desinfecção.

Extração de ferro de esmectita brasileira com emprego do método ditionito-citrato-bicarbonato

A natural clay from Campina Grande region (Paraíba, Brazil), with 8.57% of Fe2O3, was used to study the most appropriate condition to carry out the iron extraction, without altering the clay structure in a significant way. Samples were treated with the Dithionite-Citrate-Bicarbonate method (DCB) for 30 and 120 minutes (pH=9.1), and also with citric acid (pH=1.8; time=15min), at 75°C. Conductivity measurements, X-ray fluorescence, X-ray diffraction, energy-dispersive spectrometry, electron-diffraction with transmission electron microscopy and textural evaluation by nitrogen adsorption were done. The treatment in a basic medium was more selective for iron removal than in acid condition. The time of 30 minutes, with 1.6 g Na2S2O4/10 g clay, was the best condition for the iron extraction.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Extração de ferro da cera de carnaúba utilizando sistemas microemulsionados

The constant search for biodegradable materials for applications in several fields shows that carnauba wax can be a viable alternative in the manufacturing of biolubricants. Carnauba wax is the unique among the natural waxes to have a combination of properties of great importance. In previous studies it was verified the presence of metals in wax composition that can harm the oxidative stability of lubricants. Considering these factors, it was decided to develop a research to evaluate iron removal from carnauba wax, using microemulsion systems (Me) and perform the optimization of parameters, such as: extraction pH, temperature, extraction time, among others. Iron concentration was determined by atomic absorption and, to perform this analysis, sample digestion in microwave oven was used, showing that this process was very efficient. It was performed some analysis in order to characterize the wax sample, such as: attenuated total reflectance infrared spectroscopy (ATR-IR), thermogravimetry (TG), differential scanning calorimetry (DSC), energy dispersive X-ray fluorescence (EDXRF), scanning electron microscopy (SEM) and melting point (FP). The microemulsion systems were composed by: coconut oil as surfactant, n-butanol as cosurfactant, kerosene and/or heptanes as oil phase, distilled water as water phase. The pH chosen for this study was 4.5 and the metal extraction was performed in finite experiments. To evaluate Me extraction it was performed a factorial design for systems with heptane and kerosene as oil phase, also investigating the influence of temperature time and wax/Me ratio, that showed an statistically significant answer for iron extraction at 95% confidence level. The best result was obtained at 60°C, 10 hours contact time and 1: 10 wax/Me ratio, in both systems with kerosene and heptanes as oil phase. The best extraction occurred with kerosene as oil phase, with 54% iron removal

Influência do leito de contato na eficiência de remoção de ferro de águas subterrâneas

Este trabalho teve como objetivo avaliar a influência da unidade leito de contato na eficiência de remoção ferro em Estação de Tratamento de Água (ETA) tipo desferrização que trata água subterrânea. Os ensaios foram realizados em uma instalação piloto, composta por um aerador tipo tabuleiro, um leito de contato de fluxo ascendente e um filtro rápido de fluxo descendente, que tem capacidade para tratar cerca de 1,7m3/h. A ETA - piloto foi instalada no Setor Profissional do Campus Guamá da UFPA, sendo a água bruta proveniente de manancial subterrâneo, que contem ferro em teores elevados (em torno de 2mg/L). Na ETA - Piloto foram aplicadas taxas de filtração de 180m3/m2xdia, 270m3/m2xdia e 360m3/m2xdia em triplicata em duas fases experimentais: a primeira com leito de contato e segunda sem leito de contato. Foram monitoradas a carreira de filtração, a perda de carga e as variáveis: pH, Cor Aparente, Ferro (Total e Ferroso) e Turbidez. Para a Fase I as eficiências de remoção de ferro total obtidas para as taxas de filtração de 180m3/m2xdia, 270m3/m2xdia e 360m3/m2xdia foram de 93% a 94%, 85% a 95% e 91% a 92%, respectivamente. Para a Fase II as eficiências de remoção de ferro total ficaram em torno de 91% a 93%, 91% a 93% e 88% a 93%, respectivamente. As carreiras de filtração com leito de contato para as taxas de 180m3/m2xdia, 270m3/m2xdia e 360m3/m2xdia apresentaram tempo de duração média de 41h, 30h e 22,7h respectivamente, enquanto que na ausência de leito de contato a duração média foi de 16h, 12h e 4,7h, respectivamente. Dessa forma pode-se concluir que o leito de contato é uma unidade indispensável em uma ETA tipo desferrização, pois melhora o desempenho de sistema, produzindo efluente de boa qualidade e carreiras de filtração mais prolongadas.

New insights into the interactions of serum proteins with bis(maltolato)oxovanadium(IV): Transport and biotransformation of insulin-enhancing vanadium pharmaceuticals

Significant new insights into the interactions of the potent insulin-enhancing compound bis(maltolato)oxovanadium(IV) (BMOV) with the serum proteins, apo-transferrin and albumin, are presented. Identical reaction products are observed by electron paramagnetic resonance (EPR) with either BMOV or vanadyl sulfate (VOSO4) in solutions of human serum apo-transferrin. Further detailed study rules out the presence of a ternary ligand-vanadyl-transferrin complex proposed previously. By contrast, differences in reaction products are observed for the interactions of BMOV and VOSO4 with human serum albumin (HSA), wherein adduct formation between albumin and BMOV is detected. In BMOV-albumin solutions, vanadyl ions are bound in a unique manner not observed in comparable solutions Of VOSO4 and albumin. Presentation of chelated vanadyl ions precludes binding at the numerous nonspecific sites and produces a unique EPR spectrum which is assigned to a BMOV-HSA adduct. The adduct species cannot be produced, however, from a solution Of VOSO4 and HSA titrated with maltol. Addition of maltol to a VOSO4-HSA solution instead results in formation of a different end product which has been assigned as a ternary complex, VO(ma)(HSA). Furthermore, analysis of solution equilibria using a model system of BMOV with 1-methylimidazole (formation constant log K = 4.5(1), by difference electronic absorption spectroscopy) lends support to an adduct binding mode (VO(ma)(2)-HSA) proposed herein for BMOV and HSA. This detailed report of an in vitro reactivity difference between VOSO4 and BMOV may have bearing on the form of active vanadium metabolites delivered to target tissues. Albumin binding of vanadium chelates is seen to have a potentially dramatic effect on pharmacokinetics, transport, and efficacy of these antidiabetic chelates.

Utilização de quitosana obtida de resíduos de camarão para avaliar a capacidade de adsorção de íons Fe3+

A quitosana é produzida através de uma desacetilação alcalina da quitina, a qual é encontrada em exoesqueleto de crustáceos, parede celular de fungos e materiais biológicos. Calcula-se que os resíduos de camarão apresentam de 5 a 7% do seu peso total na forma de quitina, sugerindo que estes sejam utilizados para obtenção do biopolímero. Os processos para obtenção destes biopolímeros consiste nas seguintes etapas: desmineralização, desproteinização e desodorização, obtendo-se assim, a quitina úmida. Após seca, passa por uma desacetilação química para a conversão em quitosana úmida, sendo purificada e posteriormente seca. A quitosana, por apresentar grupamentos amino livres em sua estrutura, é uma molécula capaz de formar complexos estáveis com cátions metálicos. O objetivo geral deste trabalho foi obter quitina a partir de resíduos de camarão (Penaeus brasiliensis) com posterior produção de quitosana, e avaliar sua capacidade de complexação com íons Fe3+, em solução. A quitosana produzida foi caracterizada através do grau de desacetiliação e da massa molecular viscosimétrica, Para caracterização estrutural das amostras de quitosana, utilizaram-se espectrometria de infravermelho e espectrofotometria UV-Visível, bem como para o complexo formado de quitosana e ferro. Para analisar a eficiência da remoção deste íon, foram feitas análises em espectrometria de absorção atômica em chama e em espectrofotometria UV-Visível. Uma análise estatística foi realizada para avaliar a percentagem de remoção do íon ferro das soluções, sendo utilizado um planejamento fatorial em dois níveis, tendo como variáveis independentes o pH do meio, a quantidade de quitosana adicionada, a granulometria da mesma e o tempo de reação. A quitosana apresentou grau de desacetilação de 87±2% e massa molecular viscosimétrica de 196±4kDa, sendo esses valores, comparáveis à quitosana disponível comercialmente. Na melhor região de trabalho definida pela análise estatística, obteve-se uma remoção máxima de 85 % do íon ferro das soluções.

Nanosized iron based permeable reactive barriers for nitrate removal - Systematic review

It is unquestionable that an effective decision concerning the usage of a certain environmental clean-up technology should be conveniently supported. Significant amount of scientific work focussing on the reduction of nitrate concentration in drinking water by both metallic iron and nanomaterials and their usage in permeable reactive barriers has been worldwide published over the last two decades. This work aims to present in a systematic review of the most relevant research done on the removal of nitrate from groundwater using nanosized iron based permeable reactive barriers. The research was based on scientific papers published between 2004 and June 2014. It was performed using 16 combinations of keywords in 34 databases, according to PRISMA statement guidelines. Independent reviewers validated the selection criteria. From the 4161 records filtered, 45 met the selection criteria and were selected to be included in this review. This study's outcomes show that the permeable reactive barriers are, indeed, a suitable technology for denitrification and with good performance record but the long-term impact of the use of nanosized zero valent iron in this remediation process, in both on the environment and on the human health, is far to be conveniently known. As a consequence, further work is required on this matter, so that nanosized iron based permeable reactive barriers for the removal of nitrate from drinking water can be genuinely considered an eco-efficient technology.

Colour Removal From Dye-House Efiluents Using Zero-Valent iron and Fenton Oxidation

This thesis Entitled Colour removal from dye house effluents using zero valent iron and fenton oxidation.Findings reported on kinetic profile during oxidation of dyes with Fenton’s reagent are in good agreement with observations of earlier workers on other organic substrates. This work goes a step further. Critical concentration of the dye at which the reaction mechanism undergoes transition has been identified.The oxidation of Reactive Yellow showed that the initial rates for decolorization increased linearly with an increase in hydrogen peroxide concentration over the range studied. Fenton oxidation of all dyes except Methylene Blue showed that the initial rates increased linearly with an in the ferrous sulphate concentration. This increase was observed only up to an optimum concentration beyond which further increase resulted in a decrease in the initial rates. Variation of initial rates with Ferrous sulphate concentration resulted in a linear plot passing through the origin indicating that the reaction is first order with respect to ferrous sulphate.

Filtration as related to the removal of iron from ground waters /

Vita.