Many industrial processes produce effluents with a wide variety of xenobiotic organic pollutants, which cannot be efficiently degraded by conventional biological treatments. Thus, the development of new technologies to eliminate these refractory compounds in water has become very imperative in order to assure the quality of this important resource. Ozonation is a very promising process for the treatment of wastewaters containing non-easily removable organic compounds. The present work aims at highlighting new methods of enhancing the efficiency of ozone towards the removal organic pollutants in aqueous solution. Special attention is given to catalytic ozonation processes contemplating homo- and heterogeneous catalysis, their activity and mechanisms. Recent results and future prospects about the application of these processes to real effluents are also evaluated.

Cerium based-compounds have great importance in a wide range of technological applications, such as: fuel cell devices development; metallurgic processes, petroleum refining; glass and ceramic production. Recently, its catalytic properties have been also explored for environmental applications, especially those to prevent or to control atmospheric and water pollution. Subjects covered in this work include a brief description of the fundaments of cerium catalytic properties and some relevant technological applications. Special attention is given to its photocatalytic activity and its ability to degrade pollutants. Recent results and future prospect about these applications are also evaluated.

Neste trabalho é apresentado um método eficiente para a degradação de corantes, usando uma fonte de pó de ferro zero ambientalmente amigável (resíduo de um processo industrial). A influência de vários fatores experimentais (tais como: pH, massa de ferro, tamanho de partícula, concentração do substrato, atmosfera inerte ou oxidante) sobre a eficiência do ferro zero em reduzir o grupo cromóforo e o teor de carbono orgânico total de um azocorante (Preto Remazol B) foi avaliada. O processo de degradação do corante apresentou uma cinética de primeira ordem com uma constante de 0,153 min-1. Nas condições otimizadas (pH=3, [Fe] = 5 g L-1, tamanho de partícula < 250 µm), este processo promoveu uma descoloração de 95% e redução de 70% na concentração de carbono orgânico total de uma solução 100 mg L-1 do corante. Este processo também foi empregado na degradação de um efluente industrial têxtil apresentando bons resultados e demonstrando capacidade para ser uma alternativa para a remediação de sistemas aquáticos poluídos.

In this paper an efficient method for azo dye degradation using an environmentally friendly zero-valent iron powder source is presented (iron particles discarded from a manufacturing process). The influence of several experimental parameters (such as pH, iron mass, particle size, substrate concentration, oxidizing and inert atmospheres) on the ability of zero-valent iron to reduce the chromophoric groups and total organic carbon content of the azo dye Remazol Black B was evaluated. Kinetic studies revealed that the azo degradation by Fe0 appeared to be first-order with respect to substrate, with an observed rate constant (k obs) of 0.153 min-1. Under the optimized operational conditions (pH 3, [Fe] = 5 g L-1, iron particle size < 250 µm), the iron-based process produced net a reduction in color and total organic carbon of about 95% and 70%, respectively. The process was also evaluated for the degradation of textile effluent. The studied process showed good characteristics, which can make it an effective alternative for polluted aquatic system remediation.

Anthropogenic pollution of groundwater and surface water has become a very serious environmental problem around the world. A wide range of toxic pollutants is recalcitrant to the conventional treatment methods, thus there is much interest in the development of more efficient remediation processes. Degradation of organic pollutants by zero-valent iron is one of the most promising approaches for water treatment, mainly because it is of low cost, easy to obtain and effective. After a general introduction to water pollution and current treatments, this work highlights the advances, applications and future trends of water remediation by zero-valent iron. Special attention is given to degradation of organochloride and nitroaromatic compounds, which are commonly found in textile and paper mill effluents.

Tióis de cadeias carbônicas com tamanhos diferentes e contendo grupo terminal COOH foram usados para formar monocamadas auto-organizadas sobre a superfície de eletrodos de ouro. A transferência de elétrons do par Fe(CN)6(3-/4-) para o eletrodo foi estudada em diferentes pH usando-se as técnicas de voltametria cíclica (CV) e de espectroscopia de impedância eletroquímica (EIS). Mudanças no pH da solução resultaram em variações na carga do grupo terminal das monocamadas auto-organizadas e, conseqüentemente, em alterações na interação eletrostática da SAM com as espécies eletroativas em solução.

Thiols with different alkyl chain length and containing COOH terminal group were self-assembled on gold electrodes. The electron transfer of Fe(CN)6(3-/4-) couple to the electrode was studied at different pH by means cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Changes in solution pH resulted in the charge variation of the self-assembled monolayer (SAM) terminal group and, consequently, the electrostatic interaction of SAM with the electroactive species in the solution.

Self-assembled monolayers (SAMs) modified electrodes exhibit unique behavior that can greatly benefit electrochemical sensing. This brief review highlights the applications of SAM modified electrodes in electroanalytical chemistry. After a general introduction, which includes the approaches for SAM development, different electrochemical systems for detecting inorganic and organic species are described and discussed. Special attention to the coupling of biological sensing element to the SAM is given, which can selectively recognize the analyte. Future prospects are also evaluated.

A abordagem mais promissora para o desenvolvimento de biossensores eletroquímicos é a busca da comunicação elétrica direta entre as biomoléculas e a superfície do eletrodo. Esta revisão apresenta as principais abordagens, estratégias e avanços no desenvolvimento de biossensores eletroquímicos de terceira geração. Os temas discutidos englobam uma breve descrição sobre os fundamentos do fenômeno de transferência de elétrons e sobre o desenvolvimento de biossensores amperométricos (diferentes tipos e novas técnicas de imobilização orientada de enzimas). Um enfoque especial foi dado para as enzimas e proteínas redox capazes de eletrocatalisar reações via transferência direta de elétrons. Também foram apresentadas e discutidas as aplicações analíticas e tendências futuras dos biossensores de terceira geração.

The most promising approach for the development of electrochemical biosensors is to establish a direct electrical communication between the biomolecules and the electrode surface. This review focuses on advances, directions and strategies in the development of third generation electrochemical biosensors. Subjects covered include a brief description of the fundamentals of the electron transfer phenomenon and amperometric biosensor development (different types and new oriented enzyme immobilization techniques). Special attention is given to different redox enzymes and proteins capable of electrocatalyzing reactions via direct electron transfer. The analytical applications and future trends for third generation biosensors are also presented and discussed.

Desenvolveu-se um método de análise em fluxo para a determinação contínua de compostos fenólicos em matrizes ambientais, usando-se uma membrana de diálise para amostragem e biossensores a base de lacase e tirosinase para a detecção destes compostos. A resposta dos biossensores frente a diferentes compostos fenólicos foi investigada. O biossensor a base de lacase mostrou uma alta sensibilidade para guaiacol e cloroguaiacol, enquanto que o biossensor de tirosinase foi mais sensível para fenol e clorofenol. Ambos os biossensores apresentaram respostas seletivas para concentrações destes compostos em níveis micromolares. Limites de detecção de 1,1 x 10-7 mol L-1 para guaiacol e de 1,9 x 10-7 mol L-1 para cloroguaiacol foram obtidos usando-se o biossensor a base de lacase. Empregando-se o biossensor a base de tirosinase obteve-se limites de detecção de 1,5 x 10-7 mol L-1 para fenol e de 9,0 x 10-8 mol L-1 para clorofenol. O método de análise em fluxo proposto apresentou um faixa linear de trabalho entre 1,0 mimol L-1 e 100,0 mimol L-1, nas condições operacionais otimizadas dos biossensores (biossensor a base de lacase: pH 5,0 e potencial de trabalho 0 mV vs Ag/AgCl; biossensor a base de tirosinase: pH 5,0 e potencial de trabalho 50 mV vs Ag/AgCl). Uma amostra real de efluente papeleiro foi analisada pelo sistema proposto e pelo método colorimétrico de referência e os resultados discutidos.

A flow system method for continuous determination of phenolic compounds in environmental matrices was employed using a dialysis membrane sampler and laccase- and tyrosinase-based biosensors as detector. The biosensors response to different phenolic compounds was investigated. The laccase-based biosensor showed high sensitivity to guaiacol and chloroguaiacol, while the tyrosinase-based biosensor was more sensitive to phenol and chlorophenol. Both of the biosensors presented highly selective measurements of micromolar concentration of these compounds. Detection limits around 1.1 x 10-7 mol L-1 for guaiacol and 1.9 x 10-7 mol L-1 for chloroguaiacol could be estimated for the laccase-based biosensor. Using the tyrosinase-based biosensor detection limits of 1.5 x 10-7 mol L-1 for phenol and 9.0 x 10-8 mol L-1 for chlorophenol were observed. The proposed flow method presented a linear response range between 1.0 mumol L-1 and 100.0 mumol L-1, in the optimized operational conditions (laccase-based biosensor: pH 5.0 and 0 mV vs Ag/AgCl as working potential; tyrosinase-based biosensor: pH 5.5 and 50 mV vs Ag/AgCl as working potential). Real paper mill effluent sample was analyzed by this system and by the reference colorimetric method and the results were discussed.

This paper shows the assembly of an ozonization system to be used in laboratory scale, mainly to study effluent treatability. The system is simple, practical and provides easy acquisition of data when interfaced to a microcomputer. The performance of ozone generation and K La values are also described.