Distribuição de Cr, Ni, Cu, Cd e Pb em frações húmicas de diferentes tamanhos moleculares extraídas de amostras de água e de sedimentos do reservatório de captação de água superficial Anhumas - Araraquara-SP

Estudou-se a distribuição de Cr, Ni, Cu, Cd e Pb em frações de substâncias húmicas (SH) de diferentes tamanhos moleculares. As SH foram extraídas de amostras de água (SHA) e de sedimentos de superfície (SHSS), interface/água (SHSI) e fundo (SHSF) coletados no reservatório de captação de água superficial Anhumas, localizado no município de Araraquara-SP. Para a extração das SH utilizaram-se os procedimentos recomendados pela Sociedade Internacional de Substâncias Húmicas. Após purificação por diálise, as SH foram fracionadas com base no tamanho molecular utilizando-se sistema de fracionamento seqüencial por ultrafiltração e fluxo tangencial. O fracionamento das amostras de SHA permitiu caracterizar uma distribuição de massa relativamente uniforme dentre as frações de diferentes tamanhos moleculares, com valores maiores nas frações F2 (20,8%) e F4 (23,8%). Exceto para os íons Pb(II) e Cu(II) os quais apresentaram concentrações relativamente mais altas nas frações F2 e F4, respectivamente, de maneira geral, crômio, níquel, cádmio e chumbo têm distribuições similares nas cinco frações com tamanhos moleculares maiores e médios (F1 a F5). Quanto às distribuições de massa nas diferentes frações de substâncias húmicas extraídas de amostras de sedimento de superfície (SHSS), sedimento interface/água (SHSI) e sedimento de fundo (SHSF), as três amostras apresentaram 42-48% das SH nas frações com maiores tamanhos moleculares (F1 e F2), 29-31% nas frações intermediárias (F3 e F4) e 13-20% nas frações com menores tamanhos moleculares (F5 e F6). De modo geral, caracterizaram-se para os íons metálicos, distribuições similares dentre as respectivas frações F1 a F6. Exceções para Pb(II) e Ni(II) em sedimento de superfície com concentrações relativamente menores nas frações F2 e F4, respectivamente.

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.

Electrochemical properties of Cu4[PhN3C6H4N3(H)Ph]4(µ-O)2, a tetranuclear Copper(II) complex with 1-phenyltriazenido-2-phenyltriazene-benzene as ligand

Bis-(µ2-oxo)-tetrakis{[1-feniltriazene-1,3-diil)-2-(phenyltriazenil)benzene copper(II) is a tetranuclear complex which shows four Cu(II) ions coordinated by four 1,2-bis(phenyltriazene)benzene bridged ligands, with one diazoaminic deprotonated chain, and two O2- ligands. The complex reduces at E1/2 = -0.95 V vs Fc+/Fc, a two electrons process. Cyclic voltammetric and spectroelectrochemical studies showed a reversible process. When immobilized on carbon paste electrode, the complex electrocatalyses the reduction of O2 dissolved on aqueous solution at -0.3 V vs SCE potential. The obtained current shows linearity with O2 concentration.

Synthesis and magnetic studies of copper(II)-lanthanide(III) 5-bromosalicylideneglycylglycine

The physico-chemical properties of the new 3d-4f heteronuclear complexes with general formula LnCu3(C11H8N2 O4Br)3·13H2O (where Ln = Pr, Eu, Gd, Tb, Er, Yb and H3(C11H8N2 O4Br) - 5-bromosalicylideneglycylglycine) were studied. The compounds were characterized by elemental, spectral and thermal analyses and magnetic measurements. The formation of Schiff base is evidenced by a strong band at ca. 1646-1650 cm-1 attributable to C=N stretching mode. The presence of water molecules is confirmed by broad absorptions with maximum at 3360 - 3368 cm-1. The Cu(II)-Ln(III) complexes are stable up to ca. 318 K. During dehydration process the water molecules are lost probably in two stages. The magnetic susceptibility data for these complexes change with temperature according to the Curie-Weiss law.

Direct and simultaneous spectrophotometric determination of Ni (II) and Co (II) using diethanoldithiocarbamate as complexing agent

A direct spectrophotometric method for simultaneous determination of Co(II) and Ni(II), with diethanoldithiocarbamate (DEDC) as complexing agent, is proposed using the maximum absorption at 360 and 638 nm (Co(II)/DEDC) and 390 nm (Ni/DEDC). Adjusting the best metal/ligand ratio, supporting eletrolite, pH, and time of analysis, linear analytical curves from 1.0 10-6-4.0 10-4 for Co(II) in the presence of Ni 1.0 10-6-1.0 10-4 mol L-1 were observed. No further treatment or calculation processes have been necessary. Recoveries in different mixing ratios were of 99%. Interference of Fe(III), Cu(II), Zn(II) and Cd(II), and anions as NO3-, Cl-, ClO4-, citrate and phosphate has been evaluated. The method was applied to natural waters spiked with the cations.

Complexação de íons de metais por matéria orgânica dissolvida: modelagem e aplicação em sistemas reais

Os íons de metais pesados são conhecidos tanto pela sua importância fisiológica e industrial, bem como pelo risco ambiental e à saúde humana. Para elucidar o comportamento dessas espécies nos corpos hídricos, os quais recebem grande parte da descarga de metais, seja de origem antrópica ou por fontes naturais, é necessário entender as interações que elas apresentam com o meio, principalmente a especiação química. Um dos mais importantes processos pelos quais passam as espécies metálicas em corpos aquáticos naturais é a interação com a matéria orgânica dissolvida (MOD), que pode ser por adsorção, reações de troca iônica ou por complexação. Neste trabalho foram realizados vários experimentos com o objetivo de descrever o comportamento da complexação de três importantes cátions Cu(II), Cd(II) e Pb(II) com a matéria orgânica (ácido húmico comercial), sob condições diversas de força iônica em meio tamponado. Os resultados foram avaliados de acordo com o modelo de van den Berg e Kramer para a complexação de metais. O modelo foi aplicado na determinação da capacidade de complexação dos íons em amostras reais, oriundas de três rios maranhenses que integram a Amazônia legal: Itapecuru, Bacanga e Pericumã. Nas águas dos rios utilizou-se o parâmetro carbono orgânico dissolvido (COD) para expressar a MOD. Os resultados confirmaram forte interação entre a MOD e íons de metais pesados e que o modelo de van den Berg e Kramer é satisfatório para se estimar a constante de complexação (K) e a concentração de sítios de complexação (Lt). Nas amostras simuladas em laboratório a ordem de complexação dos metais foi Cu(II) > Cd(II) > Pb(II) e a capacidade de complexação mostrou ser linear em função da concentração de ácido húmico comercial. Acredita-se que por ter menor raio iônico, o íon Cu(II) possui maior afinidade com os sítios de complexação. Nas amostras retiradas dos corpos aquáticos, observou-se que o rio com maior concentração de COD (rio Bacanga) apresentou maior capacidade de complexação; entretanto, a ordem foi Pb(II) > Cu(II) > Cd(II) provavelmente devido à presença de íons Cu(II) em maior quantidade nas águas dos rios.

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.

Ultra-trace monitoring of copper in environmental and biological samples by inductively coupled plasma atomic emission spectrometry after separation and preconcentration by using octadecyl silica membrane disks modified by a new schiff's base

Ultra-trace amounts of Cu(II) were separated and preconcentrated by solid phase extraction on octadecyl-bonded silica membrane disks modified with a new Schiff,s base (Bis- (2-Hydroxyacetophenone) -2,2-dimethyl-1,3-propanediimine) (SBTD) followed by elution and inductively coupled plasma atomic emission spectrometric detection. The method was applied as a separation and detection method for copper(II) in environmental and biological samples. Extraction efficiency and the influence of sample matrix, flow rate, pH, and type and minimum amount of stripping acid were investigated. The concentration factor and detection limit of the proposed method are 500 and 12.5 pg mL-1, respectively.

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.

Quimissorção de cátions divalentes em sílica gel modificada com ácido tioglicólico: a influência do pH e força iônica

A novel type of heavy metal adsorbent was prepared by the covalent grafting of thioglycolic acid molecules on a silica gel surface previsiouly modified with 3-aminopropyltrimethoxysilane. The amount of thioglycolic acid immobilized was 1.03 mmol per gram of silica. This material displayed a chelating moiety containing nitrogen, sulfur, and oxygen basic centers which are potentially capable of extracting from aqueous solutions cations such as Cu(II), Ni(II), Co(II), influenced by pH and ionic strength. This process of extraction was carried out by the batch method when similar chemisorption isotherms were observed for all cations. A modified Langmuir equation describes the experimental data.

Propriedades ácido-base e de complexação de ácidos húmico e fúlvico isolados de vermicomposto

Proton binding properties of humic and fulvic acids were studied by potentiometric titration. Carboxylic groups were the predominant ionizable sites in comparison to phenolic and amine groups. Total acidity of fulvic acid was 12 x 10-3 mol g-1, a number significantly higher than that obtained for humic acid (5.2 x 10-3 mol g-1). Copper ion binding was evaluated at pH 4, 5 and 6 by potentiometric titration with an ion selective electrode for Cu(II). Differential stability constants and complexation capacities were systematically higher for humic acid, despite its lower number of ionizable sites in comparison with fulvic acid.

Un método de bajo costo para la determinación de cobre a nivel de vestigios en matrices de interés ambiental por espectrofotometría en fase sólida (EFS)

A method for determining copper by solid phase spectrophotometry (SPS) was optimized using the Doehlert design. Copper(II) was sorbed on a styrene-divinylbenzene anion-exchange resin as a Cu(II)-1-(2-pyridylazo)-2-naphthol (PAN) complex, at pH 7.0. Resin phase absorbances at 560 and 800 nm were measured directly. The detection limit was found to be 2.5 µg L-1. The relative standard deviation on ten replicate determinations of 10 µg Cu(II) in 1000 mL samples was 1.1%. The linear range of the determination was 5.0-100 µg L-1. The method was applied successfully to the determination of Cu(II) in natural water and vegetable samples.

Determinação voltamétrica de metais em águas e fluidos biológicos empregando mineralização de amostras com radiação ultravioleta

This work describes the optimization of pretreatment steps for the destruction of organic matter in samples of waters and biological fluids, by using an UV irradiation system with a high power UV radiation source (400 W). The efficiency of the system constructed for the photo-decomposition of samples of model waters, natural waters and biological fluids was investigated by performing recovery experiments of the metallic species Zn(II), Cd(II), Pb(II), Cu(II), Al(III) and Fe(III). The use of UV irradiation allowed the liberation of metals bound to the organic matrix and the determination of the total content of elements in the samples.

Microencapsulação do agente quelante sulfoxina em microesferas de quitosana preparadas por spray drying como novo adsorvente para íons metálicos

In this work, a new adsorbent was prepared by microencapsulation of sulfoxine into chitosan microspheres by the spray drying technique. The new adsorbent was characterized by Raman spectroscopy, scanning electron microscopy and microanalysis of energy dispersive X-rays. The Cu(II) adsorption was studied as a function of pH, time and concentration. The optimum pH was found to be 6.0. The kinetic and equilibrium data showed that the adsorption process followed the pseudo second-order kinetic model and the Langmuir isotherm model over the entire concentration range. An increase of 8.0% in the maximum adsorption capacity of the adsorbent (53.8 mg g-1) was observed as compared to chitosan glutaraldehyde cross-linked microspheres.

Estudo do comportamento eletroquímico de substâncias complexantes utilizando eletrodo de cobre

Copper electrode can be used for determination of complexing compounds through complexation reactions between Cu(II) and the analites. In this work some studies with three compounds were performed: glycine (precursor of glyphosate synthesis), herbicide glyphosate and aminomethylphosphonic acid (main metabolite of glyphosate). These compounds are complexing agents for Cu electrodes. Through simple experiments (cyclic voltammetry and corrosion studies) the applicability of the copper electrode as electrochemical sensor for complexing compounds in flow systems was presented.