Systematic studies on 3d-3d and 3d-4f multimetallic complexes with interesting magnetic and/or luminescent properties

324 p.

Root uptake and reduction of hexavalent chromium by aquatic macrophytes as assessed by high-resolution X-ray emission

Aquatic macrophytes Salvinia auriculata, Pistia stratiotes and Eichhornia crassipes were chosen to investigate the Cr(VI) reduced by root-based biosorption in a chromium uptake experiment, using a high-resolution XRF technique. These plants were grown in hydroponics medium supplied with non-toxic Cr concentrations during a 27-day metal uptake experiment. The high-resolution Cr-K beta fluorescence spectra for dried root tissues and Cr reference material (100% Cr, Cr(2)O(3), and CrO(3)) were measured using an XRF spectrometer. For all species of aquatic plant treated with Cr(VI), the energy of the Cr-K beta(2,5) line was shifted around 8 eV below the same spectral line identified for the Cr(VI) reference, but it was also near to the line identified for the Cr(III) reference. Moreover, there was a lack of the strong Cr-K beta"" line assigned to the Cr(VI) reference material within the Cr(VI)-treated plant spectra, suggesting the reduction of Cr(VI) for other less toxic oxidation states of Cr. As all Cr-K beta spectra of root tissue species were compared, the peak energies and lineshape patterns of the Cr-K beta(2,5) line are coincident for the same aquatic plant species, when they were treated with Cr(III) and Cr(VI). Based on the experimental evidence, the Cr(VI) reduction process has happened during metal biosorption by these plants. (C) 2009 Elsevier Ltd. All rights reserved.

Very low optical absorptions and analyte concentrations in water measured by Optimized Thermal Lens Spectrometry

Thermal Lens Spectrometry has traditionally been carried out in the single-beam and the mode-mismatched dual-beam configurations. Recently, a much more sensitive dual-beam TL setup was developed, where the probe beam is expanded and collimated. This feature optimizes Thermal Lens (TL) signal and allows the use of thicker samples, further improving the sensitivity. In this paper, we have made comparisons between the conventional and optimized TL configurations, and presented applications such as measurements of very low absorptions and concentrations in water and Cr(III) aqueous solution in the UV-vis range. For pure water we found linear absorption coefficients as low as the Raman scattering one due to the stretching vibrational modes of OH group. The detection limit was estimated 1 x 10(-6) cm(-1) with a 180-mW excitation power using a 100-mm cell length. This sensitivity is very high, considering that water has a photothermal enhancement factor similar to 33 times smaller than CCl(4), for example. For Cr(III) species in aqueous solution, the limit of detection (LOD) was estimated in similar to 40 ng mL(-1) at 514 nm, or similar to 10ng mL(-1) at 405 nm, which is similar to 30 times smaller than the LOD achieved with conventional transmission techniques. The more recent TL configuration is very attractive to obtain absorption spectra, since the result does not depend critically on the beam parameters, unlike the other configurations. The main drawbacks of this optimized TL configuration are the longer acquisition time and the need for larger samples. (C) 2011 Published by Elsevier B.V.

Geochemistry of natural chromium occurrence in a sandstone aquifer in Bauru Basin, Sao Paulo State, Brazil

Anomalous concentrations of Cr(VI) occur in groundwaters of the Adamantina Aquifer, in a large region in the western state of Sao Paulo, sometimes exceeding the potability limit (0.05 mg L(-1)). To identify the possible geochemical reactions responsible for the occurrence of Cr in groundwater in Urania, borehole rock samples were collected in order to carry out mineralogical and chemical analyses. In addition, multilevel monitoring wells were installed and groundwater samples were analyzed. Analyses of the borehole rock samples show the occurrence of a geochemical anomaly of Cr in the quartzose sandstones (average concentrations of 221 ppm). Chrome-diopside is one of the main minerals contributing to this anomaly, having an average Cr content of 1505 ppm. Sequential extraction experiments indicated weakly adsorbed Cr in the order of 0.54 ppm, and this quantity is enough to provide the Cr concentrations observed in groundwater. Groundwaters from the monitoring wells proved to be stratified, with the highest concentrations of Cr(VI) (0.13 mg L(-1)) being associated with high redox and pH values (over 10) and high concentrations of Na. Geochemical reactions that may explain the release of Cr from the solid phase to groundwater involve the release of Cr(III) from minerals (like chrome-diopside and Cr-Fe hydroxide), followed by oxidation of Cr(III) to Cr(VI), probably related to the reduction of Mn oxides present in the aquifer. Then cation exchange occurs and dissolution of carbonates which increases the pH of groundwater, resulting in the desorption and mobilization of Cr(VI) into groundwater. (C) 2011 Elsevier Ltd. All rights reserved.

The influence of albumin on the anodic dissolution of chromium present in UNSS31254 stainless steel in chloride environment

The influence of bovine serum albumin (BSA) on the anodic dissolution of chromium present in UNS S31254 stainless steel (SS) in 0.15 mol L-1 NaCl at 37.0 +/- 0.5 degrees C has been studied, using anodic potentiostatic polarization curves and optical emission spectroscopy. Electrochemical results have shown that BSA has little effect on the transpassivation potential (E-T) and on the passivation current density values. However on the passivation range, BSA diminishes the intensity of the anodic wave seen at about E=750mV versus SCE attributed to Cr(III)/Cr(VI) oxidation. Optical emission spectroscopy results have shown that BSA prevents the anodic dissolution of chromium to occur and minimizes iron dissolution above the transpassivation potential (E=1160 mV versus SCE). (C) 2007 Elsevier B.V. All rights reserved.

Determinação das espécies de cromo nas cinzas da incineração de couro wet-blue em reatores de leito fixo e leito fluidizado

Este trabalho tem como objetivo a determinação quantitativa da concentração de cromo (III, VI e total) nas cinzas de serragem de couro wet-blue, incineradas em reatores de leito fixo nas temperaturas de 450, 550 e 650 C e reator de leito fluidizado nas temperaturas de 730, 780, 830 e 850 C, verificando se estes resultados estão dentro dos limites permitidos pelas normas ambientais brasileiras e, consequentemente, se em relação à concentração de cromo, os processos de incineração utilizados são uma maneira adequada de promover a eliminação ambientalmente aceitável da serragem de couro wet-blue. Realizou-se, neste trabalho, o estudo dos procedimentos para digestão da amostra, dos métodos analíticos quantitativos para a determinação da concentração de cromo que constatou-se depender da valência a ser analisada. As determinações de cromo total e cromo hexavalente contido nas cinzas foram realizadas após digestão ácida e digestão alcalina da amostra, respectivamente. Após o processo de digestão o cromo total (na forma de Cr (VI)) e o cromo hexavalente foram determinados por dois métodos espectrofotométricos na forma de Cr (VI) em meio ácido com difenilcarbazida (DPC) e após redução na forma de Cr (III), complexado com EDTA. O cromo total também foi determinado por volumetria empregando o método titulométrico. Este método não foi empregado na determinação de cromo hexavalente devido aos baixos teores deste nas cinzas. O teor de Cr (III) foi obtido pela diferença entre o cromo total e cromo hexavalente Procedendo-se a análise estatística dos resultados de cromo hexavalente e total nas cinzas pelos diferentes técnicas analíticas, independente do tipo de incinerador, verificou-se que não há diferenças significativas entre os mesmos. Podendo, portanto, utilizar quaisquer uma das técnicas para avaliá-los. Comparando-se os resultados das análises obtidos na incineração da serragem de couro wet-blue em reator de leito fixo e reator de leito fluidizado em diferentes temperaturas, verificou-se que no reator de leito fixo o teor de Cr (VI) nas cinzas geradas foi muito baixa, praticamente inexistente; enquanto que no reator de leito fluidizado se a temperatura de combustão não for muito alta o teor de Cr (VI) ficará dentro dos limites aceitáveis. As cinzas provenientes de qualquer um dos processos de incineração analisadas, neste trabalho, tanto do reator de leito fixo como de leito fluidizado não é conveniente que seja descartada diretamente no solo. As mesmas devem ser aproveitadas na indústria de cerâmicos, ou mesmo em algum processo que visa recuperar o cromo.

Isolamento de bactérias resistentes a cromo hexavalente e purificação parcial da enzima redutora de cromo do Bacillus sp. ES29

A redução do Cr(VI) para Cr(III) diminui a toxidade deste metal no ambiente uma vez que, o Cr(III) é insolúvel às membranas biológicas. Assim a redução microbiana do Cr(VI) é uma alternativa para reduzir os impactos ambientais causados por este metal, utilizado em diversos processos industriais. O objetivo deste trabalho foi selecionar microrganismos a partir de solo contaminado com cromo, caracterizar sua capacidade de redução do Cr(VI) durante o crescimento celular e purificar parcialmente a enzima cromo redutase do Bacillus sp. ES29, através da precipitação com sulfato de amônio (45-75%), cromatografia de gel filtração (Sephadex G-25) e cromatografia de interação hidrofóbica (Octyl Sepharose). A atividade de redução do Cr(VI) pelos isolados foi quantificada com o reagente de s-difenilcarbazida. No isolamento, foram obtidas 20 bactérias resistentes a cromo(VI). Seis destas foram capazes de reduzir 100 mg L-1 Cr(VI) em 24 horas. Um dos isolados foi identificado, através de testes bioquímicos, como pertencete ao gênero Bacillus, sendo tolerante a 750 mg L-1 Cr(VI) e reduzindo mais de 40% do Cr(VI) durante o crescimento celular. Na purificação parcial da enzima foi obtido um fator de purificação de 11,2, aumentando a atividade específica da enzima acima de 11 vezes, porém se faz necessário mais passos de purificações para obtenção desta enzima pura. As bactérias selecionadas e a enzima parcialmente purificada, foram eficientes na redução do Cr(VI) e apresentam potencial para outros estudos, visando a aplicação em processos de biorremediação.

Utilização de microemulsões como agentes modificadores de superfícies para remoção de íons metálicos

The heavy metals are used in many industrial processes and when discharged to the environment can cause harmful effects to human, plants and animals. The adsorption technology has been used as an effective methodology to remove metallic ions. The search for new adsorbents motivated the development of this research, accomplished with the purpose of removing Cr (III) from aqueous solutions. Diatomite, chitosan, Filtrol 24TM and active carbon were used as adsorbents. To modify the adsorbent surface was used a bicontinuous microemulsion composed by water (25%), kerosene (25%), saponified coconut oil (10%) and as co-surfactant isoamyl or butyl alcohols (40%). With the objective of developing the best operational conditions the research started with the surfactant synthesis and after that the pseudo-ternary diagrams were plotted. It was decided to use the system composed with isoamyl alcohol as co-surfactant due its smallest solubility in water. The methodology to impregnate the microemulsion on the adsorbents was developed and to prepare each sample was used 10 g of adsorbent and 20 mL of microemulsion. The effect of drying time and temperature was evaluated and the best results were obtained with T = 65 ºC and t = 48 h. After evaluating the efficiency of the tested adsorbents it was decided to use chitosan and diatomite. The influence of the agitation speed, granule size, heavy metal synthetic solution concentration, pH, contact time between adsorbent and metal solution, presence or not of NaCl and others metallic ions in the solution (copper and nickel) were evaluated. The adsorption isotherms were obtained and Freundlich and Langmuir models were tested. The last one correlated better the data. With the purpose to evaluate if using a surfactant solution would supply similar results, the adsorbent surface was modified with this solution. It was verified that the adsorbent impregnated with a microemulsion was more effective than the one with a surfactant solution, showing that the organic phase (kerosene) was important in the heavy metal removal process. It was studied the desorption process and verified that the concentrated minerals acids removed the chromium from the adsorbent surface better than others tested solutions. The treatment showed to be effective, being obtained an increase of approximately 10% in the chitosan s adsorption capacity (132 mg of Cr3+ / g adsorbent), that was already quite efficient, and for diatomite, that was not capable to remove the metal without the microemulsion treatment, it was obtained a capacity of 10 mg of Cr3+ / g adsorbent, checking the applied treatment effectiveness

Study on soluble heavy metals with preconcentration by using a new modified oligosilsesquioxane sorbent

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

Flame AAS determination of metal ions in fuel ethanol after preconcentration on acid carboxymethylcellulose (CMCH)

This paper describes the preparation of acid carboxymethylcellulose (CMCH), and the results of a study on the adsorption and preconcentration (using batch and flow-through column methods) of Cd(II), Cu(II), Cr(III), Fe(III), Ni(II) and Zn(II) in ethanol medium. The adsorption capacities for each metallic ion were (in mmol g(-1)) Cd(II) = 0.92; Cu(II) = 1.45; Cr(III) = 1.70; Fe(III) = 1.60; Ni(II) = 1.30; and Zn(II) = 1.10. By means of the flow-through method, a recovery of ca. 100% of the metallic ions adsorbed in a column packed with 2 g of CMCH was found when 5.0 mL of 1.0 mol L-1 hydrochloric acid were used as eluent. An enrichment factor of 20 (100 mt solution containing 50 mu g L-1 of the metallic ions, concentrated to 5.0 mt) was obtained by this preconcentration procedure. The sorption-desorption procedure applied allowed the development of a preconcentration and Flame AAS quantification method of metallic ions in fuel ethanol at trace levels.

Spectroscopic characterization of the reduction and removal of chromium (VI) by tropical peat and humin

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Simultaneous removal of chromium and leather dye from simulated tannery effluent by photoelectrochemistry

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

Redução de crômio hexavalente por substâncias húmicas aquáticas imobilizadas em aminopropil sílica

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

Development of a voltammetric sensor for chromium(VI) determination in wastewater sample

Screen-printed carbon electrode (SPCE) modified with poly-L-histidine film can be successfully applied for chromium(VI) determination based on its pre-concentration. Optimum adherence and stability of the POIY-L-histidine film was obtained by direct addition of PH solution 1% (w/v) on the electrode surface, followed by heating at 80 degrees C during 5 min. Linear response range, sensitivity and limit of detection were 0. 1-150 [mu mol L-1, 4. 13 LA mu mol L` and 0.046 mu mol L-1. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation, was measured as 3.2% for 10 experiments in 40 mu mol L-1 using the same electrode and 4.0% using screen-printed electrode as disposable sensor, respectively. The voltammetric sensor was applied to determination of Cr(VI) and indirect determination of Cr(III) in wastewater samples previously treated by a leather dyeing industry and the average recovery for these samples was around 97%. (C) 2006 Elsevier B.V. All rights reserved.

Synthesis, characterization and electrochemical study of layered double hydroxides intercalated with 2-thiophenecarboxylate anions

The synthesis, characterization, and electrochemical study of the Zn(II)-Al(III) and Zn(II)-Cr(III) Layered Double Hydroxides (LDHs) containing 2-thiopenecarboxylate as the interlayer anions are described. The LDHs were prepared by the constant pH coprecipitation technique followed by hydrothermal treatment for 72 h. The materials were analyzed by PXRD, FT-IR, C-13 CP-MAS, EDX, TEM, and CV. The presence of the organic heterocyclic anions was confirmed by FT-IR and the related solid-state C-13 NMR data strongly suggested that these were dimerised during coprecipitation. Accordingly, the basal spacing found by the X-ray technique was similar to 15.3 Angstrom, a distance coincident with the formation of bilayers of the intercalated anions. The structural organization of all the new materials was greatly enhanced by hydrothermal treatment, as shown by PXRD. The improved organization of the bilayered structures had a strong influence in the electrochemical behaviour of clay-modified electrodes produced with these materials, such as the diminished resistance to the ionic flow through the LDHs films. (C) 2003 Elsevier Ltd. All rights reserved.