ABSTRACT Coagulation-flocculation (CF) process studies on aqueous solutions of Acid Black 210 dye (AB-210), were performed to investigate efficiency at different pH, coagulant and polyelectrolyte doses, and sedimentation times. In the adsorption studies of the dye removal, the initial pH and isotherms studies were performed using an activated carbon prepared by microwave-assisted pyrolysis of Tannery sludge. This adsorbent material was characterized by isotherms of N2 adsorptiondesorption and density functional theory. Finally, the efficiency of the combined process CF followed by adsorption, was shown using a synthetic effluent identical to that produced in the wet-end process of the leather industry in industrial equipment. Effluent was collected from each treatment bath and analyzed for its physical properties and by ion chromatography. The best conditions found in CF processes were: pH 10.0, sedimentation time of 60 minutes, coagulant dose of 71 mg L-1 (Al2SO4)3) and dose of flocculant (polyelectrolyte FX AS1) of 0.090 mg L-1 In the adsorption processes, the equilibrium data were best fit to the Liu isotherm model, presenting the maximum sorption capacity (Qmax) for AB-210 of 974.7 mg g-1 at 303.15K at pH 2.0. Using the synthetic effluent, the combined CF followed by adsorption of AB-210 dye demonstrated a removal of 85.2%, indicating that the combined process is efficient for real wastewater treatment.

In this paper a novel adsorbent was prepared from Nigella sativa L. waste and used for the removal of Coomassie Brilliant Blue dye from wastewater. The preparation of Nigella sativa waste carbon (NSWC) was achieved by adding concentrated sulfuric acid to the precursor material at an impregnation ratio (1: 1) and the mixture was left overnight. The resulting material was washed with sodium bicarbonates and finally oven dried. The kinetics of coomassie brilliant blue adsorption onto NSWC was investigated by three kinetic models. The pseudo-second order model (R² = 0.99) was the best model fitted the experimental data. The equilibrium results revealed that Freundlich model was the best isotherm model fitted (R²= 0.994). Also the value of the Freundlich exponent (n) was found to be 1.174 suggesting the favorable dye adsorption onto NSWC. The thermodynamics results indicated negative values of ΔG proving the spontaneous nature of Brilliant Blue dye adsorption on NSWC. The exothermic nature of the adsorption was also confirmed by the negative value of change in enthalpy ΔH°. Also, the negative value of the activation entropy ΔS° demonstrates the decreased randomness at the solid-solution interface during adsorption. The present study results suggest the possible use of a waste such as Nigella sativa L. waste as a precursor for the development of a new cheap and efficient adsorbent that could be used in dyes removal from wastewater.

A novel carbon composite was prepared from a mixture of coffee waste and clay with inorganic:organic ratio of 1.3 (CC-1.3). The mixture was pyrolysed at 700 °C. Considering the application of this adsorbent for removal of anionic dyes, the CC-1.3 was treated with a 6 mol L-1 HCl for 24 h to obtain ACC-1.3. Fourier transform infrared (FTIR), N2 adsorption/desorption curves, scanning electron microscope (SEM) and powder X-ray diffractometry (XRD) were used for characterisation of CC-1.3 and ACC-1.3 carbon adsorbents. The adsorbents were effectively utilised for removal of reactive blue 19 (RB-19) and reactive violet 5 (RV-5) textile dyes from aqueous solutions. The maximum amounts of RB-19 dye adsorbed at 25 °C are 63.59 (CC-1.3) and 110.6 mg g-1 (ACC-1.3), and 54.34 (CC-1.3) and 94.32 mg g-1 (ACC-1.3) for RV-5 dye. Four simulated dye-house effluents were used to test the application of the adsorbents for treatment of effluents.

Multi-walled and single-walled carbon nanotubes were used as adsorbents for the removal of Reactive Blue 4 textile dye from aqueous solutions. The adsorbents were characterised using Raman spectroscopy, N2 adsorption/desorption isotherms and scanning and transmission electron microscopy. The effects of pH, agitation time and temperature on adsorption capacity were studied. In the acidic pH region, the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium isotherms at 298-323 K was fixed at 4 hours for both adsorbents. For Reactive Blue 4 dye, Liu isotherm model gave the best fit for the equilibrium data. The maximum sorption capacity for adsorption of the dye occurred at 323 K, attaining values of 502.5 and 567.7 mg g-1 for MWCNT and SWCNT, respectively.

Neste trabalho, o corante azul de metileno foi imobilizado na superfície do acetato de celulose modificado com dióxido de titânio produzindo um material híbrido sólido denominado de CA-TiO2MB. O experimento produziu uma quantidade de 1,8 mmol g-1 de TiO2 incorporado no acetato de celulose e uma quantidade de 0,170 ± 0,005 mmol g-1 de azul de metileno adsorvido na superfície do CA-TiO2. Um eletrodo de pasta de carbono desse material foi usado para estudar a oxidação eletrocatalítica do ácido ascórbico pelas técnicas de voltametria cíclica e cronoamperometria. O pH da solução não afetou o potencial de pico de anódico nem a corrente de pico anódico ao variar de 3,0 a 7,0. A oxidação do analito ocorreu em 75 mV versus ECS em solução de KCl 1,0 mol L-1 e pH 7,0. A intensidade da corrente de pico anódico variou com a concentração de ácido ascórbico na faixa de 5,0 × 10-4 mol L-1 to 4,5 × 10-3 mol L-1, sendo observada uma correlação linear com um limite de detecção de 15 µmol L-1, limite de quantificação de 50 µmol L-1 e uma sensibilidade de 7,1 µA L mol-1. A resposta do eletrodo foi muito rápida, com um tempo decorrido de 1,0 s, mostrando potencial para ser utilizado como um sensor eletroquímico para a determinação de ácido ascórbico em produtos comerciais.

In this work, methylene blue dye was immobilized on the surface of cellulose acetate modified with titanium dioxide, producing a solid hybrid material designated as CA-TiO2MB. The experiment yielded an amount of 1.8 mmol g-1 of TiO2 incorporated in the cellulose acetate and an amount of 0.170 ± 0.005 mmol g-1 of methylene blue adsorbed onto CA-TiO2 surface. A carbon paste electrode of this material was used to study the electrocatalytic oxidation of ascorbic acid by cyclic voltammetric and chronoamperometric techniques. The pH of the solution had no effect on the anodic peak potential and anodic peak current when ranging from 3.0 to 7.0. The oxidation of the analyte occurred at 75 mV versus SCE in 1.0 mol L-1 KCl solution and pH 7.0. The intensity of the anodic peak current varied with the concentration of ascorbic acid from 5.0 × 10-4 mol L-1 to 4.5 × 10-3 mol L-1 and a linear correlation was observed, with a detection limit of 15 µmol L-1, quantification limit of 50 µmol L-1 and a sensitivity of 7.1 µA L mol-1. The electrode response was very fast, with an elapsed time of about 1.0 s, showing the potentiality to be utilized as an electrochemical sensor for determination of ascorbic acid in commercial samples.

In order to reduce the total number of experiments for achieving the highest amount of adsorbed Cu2+ (qmax) using pecan nutshells (Carya illinoensis) as biosorbent, a full 2(4) factorial design with two central points was carried out (mass of biosorbent- m, pH, initial metallic ion concentration- C0, time of contact- t). In order to continue the optimization of the system, a central composite surface analysis design with two factors and five central points was carried out. The maximum amount of Cu2+ taken up by the pecan nutshells was 20 mg g-1. These results were confirmed by determining a Cu2+ isotherm using the best conditions attained by the statistical design of experiments.

As propriedades eletroquímicas dos corantes catiônicos, azul de meldola e azul de toluidina, imobilizados na superfície do acetato de celulose modificado com dióxido de titânio foram investigadas por voltametria cíclica. Os materiais sintetizados foram empregados como eletrodos de pasta de carbono. As propriedades mediadoras redox dos eletrodos modificados quimicamente com azul de meldola e azul de toluidina foram otimizadas utilizando um planejamento fatorial consistindo de dois níveis e quatro fatores com dois pseudo-pontos centrais (n=20 experimentos). A análise fatorial foi realizada para investigar as melhores condições de reversibilidade do processo redox tais como uma diminuição na separação entre os picos de potenciais anódico e catódico e razão de corrente próxima da unidade. Os fatores que apresentaram efeitos significantes na otimização global do sistema e que permitiram alcançar as melhores condições de reversibilidade de transferência de elétrons foram os fatores principais velocidade de varredura e tipo de eletrodo (azul de meldola ou azul de toluidina) além dos fatores de interação concentração do KCl × tipo de eletrodo (B×D) e a interação pH × [KCl] × velocidade de varredura (A×B×C). As melhores condições de reversibilidade eletroquímica obtidas foram: o eletrodo CA-TiO2-MB, KCl 1,0 mol L-1 como eletrólito suporte e velocidade de varredura de 10,0 mV s-1. Adicionalmente, o eletrodo modificado CA-TiO2-MB foi testado como sensor amperométrico para a determinação de NADH com um limite de detecção de 0,1 µmol L-1.

The electrochemical properties of meldola blue and toluidine blue cationic dyes immobilized on cellulose acetate surface modified with titanium dioxide were investigated by cyclic voltammetry. The materials synthesized were employed as carbon paste electrodes. The redox mediator properties of the meldola blue and toluidine blue chemically modified electrodes were optimized using a factorial design, consisting of two levels and four factors with two pseudo-central points (n= 20 experiments). The factorial analysis was carried out by searching for better reversibility of the redox process, such as the lowest separation between anodic and cathodic potential peaks and a current ratio near unity. The factors that presented significant effects on the overall optimization of the system to achieve the best conditions of the reversibility of electron transfer were the main factors scan rate and type of electrode (meldola blue or toluidine blue), besides the interaction factors KCl concentration × type of electrode (B×D) and the pH × [KCl] concentration × scan rate (A×B×C) interaction. The best electrochemical reversibility conditions obtained were: using the CA-TiO2-MB electrode, 1.0 mol L-1 KCl as supporting electrolyte, at scan rate of 10.0 mV s-1. Afterwards, the CA-TiO2-MB modified electrode was tested as an amperometric sensor for the determination of NADH, with a detection limit of 0.1 µmol L-1.

The electrochemical properties of methylene blue immobilized on cellulose/TiO2 and mixed oxide SiO2/TiO2 matrices were investigated by means of cyclic voltammetry. The electron mediator property of the methylene blue was optimized using a factorial design, consisting of four factors in two levels. The experimental observations and data analyses on the system indicate that the lowest peak separation occurs for Sil/TiOAM, 1.0 mol L-1 KCl solution and 20 mV s-1 scan rate, while values of current ratio closest to unity were found for Cel/TiOAM independent of electrolyte concentration, 0.2 or 1.0 mol L-1, and scan rate, 20 mV s-1 or 60 mV s-1.