Extração de Al(III), Cr(III) e Fe(III) de meio etanólico usando o xerogel anilinapropilsílica

In this study, the preparation of the xerogel anilinepropylsilica is reported. The ability of the xerogel for extracting Al(III), Cr(III) and Fe(III) from ethanol was investigated at 25 ºC. The xerogel adsorption capacities were obtained from the adsorption isotherms by using the batch method. Flame atomic absorption spectrometry (FAAS) was used to estimate the concentration of metal ions in solution. The adsorption affinity follows the series Cr(III) > Fe(III) > Al(III) and the maximum adsorption capacities of the metal ions were 0.61, 0.52 and 0.43 mmol g-1, respectively.

Pré-concentração de Cr(III) e análise de especiação de cromo empregando montmorilonita saturada com íons potássio

The clay mineral montmorillonite-K10 (MT), treated under acidic medium and saturated with potassium ions (MTK), was employed in sorption and desorption studies aiming the preconcentration of Cr(III) and the speciation analysis of chromium. The sorption process of Cr(III) was close to 100%, suggesting that MTK was a good material for Cr(III) preconcentration, although, the maximum recovery in HNO3 solution was near 89%. On the other hand, Cr(VI) practically was not retained in MTK, suggesting this material as an appropriate mineral phase to be used in speciation analysis of chromium in aqueous medium.

Estudo comparativo da seletividade de um método cinético-catalítico: a determinação de Cr(VI) pela oxidação da o-dianisidina pelo peróxido de hidrogênio

Selectivity studies for the determination of Cr(VI) using the catalytic oxidation of the o-dianisidine by hydrogen peroxide showed two distincts situations. In the first, when interferents were studied by a univariate procedure, Cr(III) and Cu(II) cause serious interferences even at the 2:1 proportion, relative to Cr(VI), while Fe(III) interfered at the 15:1 ratio and EDTA at the 10:1 ratio. On the other hand, when a multivariate investigation was performed, Cr(III) did not present any significant principal effects and its significant interaction effects were negative, in contrast to EDTA, that presented positive interaction effects although, like Cr(III), did not show significant interaction effects. In view of the interferent's action it become necessary to separate Cr(VI) by extraction with methylisobutylketone in a chloridric acid medium before its determination in vegetals and in wastewater from a cellulose industry samples. Using this procedure, the method precision is ±0,5% at the 10 ng/mL Cr(VI) concentration level. The detection and quantification limits, calculated by means of absorbance measurements of ten replicates of blank reagents were 1,1 and 3,2 ng/mL, respectively. The results obtained with real samples showed a relative standard deviation between 1,2% and 3,0% relative to their reference values.

Lability of Cd, Cr, Cu, Mn and Pb complexed by aquatic humic substances

The lability of Cd(II), Cr(III), Cu(II), Mn(II) and Pb(II) complexed by humic substances (HSs) was investigated by means of ion exchange on cellulose modified with p-aminobenzoic groups (Cell-PAB), using a batch procedure. The HSs were extracted from water samples using adsorption in a column packed with XAD 8 resin. The metal-HS complexes were prepared by adding solutions containing all the aforementioned metal ions ( Cd(II), Cr(III), Cu(II), Mn(II) and Pb(II) ). The results indicated that the distribution coefficients (Kd) of Cell-PAB decreased with the presence of HSs, and that the lability of metal fractions complexed by HSs decreases in pH values > 4.0, complexation time > 10 h and HS concentration > 500 mg L-1. The metal exchange between HSs and Cell-PAB exhibited the following order of metal ion lability: Cd < Pb < Mn @ Cr < Cu.

Utilização de resíduos da indústria de couro como fonte nitrogenada para o capim-elefante

Uma grande variedade de produtos tóxicos é emitida durante o processo de tratamento do couro nos curtumes que usam o cromo III para obter o couro wet blue. O resíduo sólido (raspas e aparas) contém cerca de 3 % de Cr III, que representa um sério problema ambiental e não tem, atualmente, destino adequado. O resíduo de couro após extração de Cr (colágeno) foi utilizado como fonte nitrogenada para o capim-elefante (Pennisetum purpureum Schum cv. Napier), em um Latossolo Vermelho-Amarelo, aplicando-se quatro doses do colágeno (4, 8, 16 e 32 t ha-1) e três tratamentos adicionais (testemunha; adubação com N mineral e resíduo de couro wet blue- sem a extração do Cr). O colágeno é uma boa fonte nitrogenada alternativa para crescimento do capim-elefante até a dose de 16 t ha-1. O resíduo de couro wet blue não disponibilizou N durante o cultivo de capim-elefante. Isso mostra que a extração do Cr utilizando-se o ácido fosfórico é fundamental para uso do rejeito de couro como fonte nitrogenada na agricultura. A aplicação do colágeno supriu a necessidade de N para plantas de capim-elefante, semelhantemente à adubação com N mineral.

Tannery and coal mining waste disposal on soil

Tannery residues and coal mine waste are heavily polluting sources in Brazil, mainly in the Southern States of Rio Grande do Sul and Santa Catarina. In order to study the effects of residues of chrome leather tanning (sludge and leather shavings) and coal waste on soybean and maize crops, a field experiment is in progress since 1996, at the Federal University of Rio Grande do Sul Experimental Station, county of Eldorado do Sul, Brazil. The residues were applied twice (growing seasons 1996/97 and 1999/00). The amounts of tannery residues were applied according to their neutralizing value, at rates of up to 86.8 t ha-1, supplying from 671 to 1.342 kg ha-1 Cr(III); coal waste was applied at a total rate of 164 t ha-1. Crop yield and dry matter production were evaluated, as well as the nutrients (N, P, K, Ca, Mg, Cu and Zn) and Cr contents. Crop yields with tannery sludge application were similar to those obtained with N and lime supplied with mineral amendments. Plant Cr absorption did not increase significantly with the residue application. Tannery sludge can be used also to neutralize the high acidity developed in the soil by coal mine waste.

Uso de irradiação de microondas na determinação espectrofotométrica de cromo com EDTA

Cr(III) slowly forms a violet complex with EDTA at pH 2.5-5.0 under normal conditions. The complex formation can be accelerated by irradiating the reacting mixture with microwave energy. The complex Cr(III)-EDTA is completely formed within 3 minutes of microwave irradiation and followed by a simple and rapid method for spectrophotometric determination of chromium. The method may be successfully applied to determination of chromium in catalyst.

Remoção de metais pesados de efluentes aquosos pela zeólita natural escolecita - influência da temperatura e do pH na adsorção em sistemas monoelementares

Cation exchange capabilities of a Brazilian natural zeolite, identified as scolecite, were evaluated for application in wastewater control. We investigated the process of sorption of chromium(III), nickel(II), cadmium(II) and manganese(II) in synthetic aqueous effluents, including adsorption isotherms of single-metal solutions. The natural zeolite showed the ability to take up the tested heavy metals in the order Cr(III) > Cd(II) > Ni(II) > Mn(II), and this could be related to the valence and the hydration radius of the metal cations. The influence of temperature (25, 40 and 60 ºC) and initial pH value (from 4 to 6) was also evaluated. It was found that the adsorption increased substantially when the temperature was raised to 60 ºC and that maximum adsorption capacity was observed at pH 6. These results demonstrate that scolecite can be used for removal of heavy metals from aqueous effluents, under optimized conditions.

Complexos metálicos com o herbicida glifosato: revisão

We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature.

A novel method for fast enrichment and monitoring of hexavalent and trivalent chromium at the ppt level with modified silica MCM-41 and its determination by inductively coupled plasma optical emission spectrometry

Chromium(III) at the ng L-1 level was extracted using partially silylated MCM-41 modified by a tetraazamacrocyclic compound (TAMC) and determined by inductively coupled plasma optical emision spectrometry (ICP OES). The extraction time and efficiency, pH and flow rate, type and minimum amount of stripping acid, and break- through volume were investigated. The method's enrichment factor and detection limit are 300 and 45.5 pg mL-1, respectively. The maximum capacity of the 10 mg of modified silylated MCM-41 was found to be 400.5±4.7 µg for Cr(III). The method was applied to the determination of Cr(III) and Cr(VI) in the wastewater of the chromium electroplating industry and in environmental and biological samples (black tea, hot and black pepper).

Especiação redox de cromo em solo acidentalmente contaminado com solução sulfocrômica

Determination of Cr(VI) and Cr(III) was studied in soil samples accidentally contaminated with sulphochromic solution. Molecular absorption spectrophotometry based on the diphenylcarbazide method was used for the determination of Cr(VI) after its alkaline extraction. The total chromium concentration was determined using ICP OES. The quantification of Cr(III) was accomplished by subtracting the Cr(VI) concentration from the total chromium concentration. Regardless of the known contamination of the soil samples by sulphochromic solution, concentrations of Cr(VI) were below the detection limit. Addition and recovery experiments for Cr(VI) in soil samples with and without organic matter indicated its influence on the reduction of Cr(VI) to Cr(III).

Especiação de cromo em cimentos e derivados de cimento brasileiros

A method for determination of Cr(III) and Cr(VI) in cement and cement-related materials was studied. Molecular absorption spectrophotometry based on 1,5-diphenylcarbazide as chromogenic reagent was used for determination of Cr(VI) after alkaline extraction. The total chromium concentration was determined using flame atomic absorption spectrometry (FAAS) after complete sample decomposition by fusion. The quantification of Cr(III) was accomplished by subtracting the Cr(VI) concentration from the total chromium concentration. The concentration of Cr(III) in the samples ranged from 10.9 to 88.0 mg kg-1, whereas only in few samples the Cr(VI) concentration was higher than the value established by the European Community to this type of sample [2 mg kg-1 Cr(VI)].

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

Estudou-se a redução de Cr(VI) à Cr(III) utilizando-se um novo suporte preparado pela ativação de aminopropil sílica com substâncias húmicas aquáticas (ATPS-SiO2-SHA). Coletaram-se amostras de água no Corrégo Itapitangui localizado no município de Cananéia-SP e extraíram-se as SHA utilizando-se procedimento recomendado pela Sociedade Internacional de Substâncias Húmicas. Após purificação por diálise, fez-se a imobilização das SHA na aminopropil sílica (APTS-SiO2) em pH 7,0, sob agitação mecânica por 48 horas à temperatura ambiente. Adicionaram-se 150 mg de APTS-SiO2-SHA à 150 mL de soluções 9,5 mimol L-1 de Cr(VI), fixou-se o pH em 2,5, 4,5 e 6,0 e mantiveram-se as misturas sob agitação mecânica à temperatura ambiente. Coletaram-se alíquotas em função do tempo (0-72 horas) e as concentrações de Cr(VI) foram determinadas por espectrofotometria baseada na reação com 1,5-difenilcarbazida. A porcentagem de redução de Cr(VI) por APTS-SiO2-SHA foi de 50, 4 e 0 % em pH 2,5, 4,5 e 6,0, respectivamente. Dobrando a massa do suporte APTS-SiO2-SHA verificou-se em pH 2,5, a redução de 70 % de Cr(VI). Esses resultados preliminares mostram forte influência do pH e da quantidade de APTS-SiO2-SHA no processo de redução do Cr(VI). Após outros estudos, a utilização do suporte APTS-SiO2-SHA pode ser uma alternativa viável a ser aplicada para o tratamento de resíduos e/ou estudos de especiação de crômio.

Aplicação da zeólita natural escolecita na remoção de metais pesados de efluentes industriais: competição entre os cátions e processo de dessorção

Efluentes aquosos industriais são a principal causa de contaminação das águas com metais pesados. Diante de uma legislação cada vez mais rígida para o descarte desses metais, o desenvolvimento de procedimentos eficientes e de baixo custo para o tratamento de efluentes contendo metais pesados torna-se de grande interesse. Um estudo sobre a capacidade de retenção de metais pesados pela zeólita natural escolecita foi realizado, de modo a se avaliar a viabilidade desta aplicação. Os cátions utilizados foram Mn(II), Cd(II), Ni(II) e Cr(III). Nesta etapa do trabalho, foi avaliado o comportamento da zeólita na adsorção seletiva de cátions presentes nos pares Cd/Mn, Cr/Ni, Cr/Cd e Ni/Mn, bem como a possibilidade de dessorção dos cátions metálicos adsorvidos em sua estrutura. A escolecita apresentou uma seletividade que pode ser relacionada, na maioria dos casos, à valência e ao raio iônico das espécies hidratadas. Os cátions Cr(III) e Ni(II) foram fortemente adsorvidos, não podendo ser substancialmente removidos por troca com cátions sódio ou cálcio. Dos cátions testados, apenas o Cd(II) apresentou comportamento de adsorção e de dessorção atípicos, demonstrando uma elevada labilidade no processo de troca iônica.

Preparation and evaluation of magnetic chitosan particles modified with ethylenediamine and Fe(III) for the removal of Cr(VI) from aqueous solutions

The adsorption of Cr(VI) in aqueous solution by magnetic particles of crosslinked chitosan-ethylenediamine-Fe(III) (MPCh-EDA-FeCL) was studied in a batch system. Fe3+ in the MPCh-EDA-FeCL permitted that adsorption of Cr(VI) occurred with maximum efficiency between pH 3 and 11. The maximum adsorption capacity at pH 7.0 was 81.04 mg g-1 at 25 ºC. The adsorption kinetic process was described by the pseudo-second-order model. Thermodynamic parameters indicated spontaneous, exothermic and chemical adsorption nature. The adsorbent was successively regenerated using a 0.1 mol L-1 NaOH solution. Results were satisfactory for treatment of wastewater from the electroplating industry.