Removal of dyes from water using Citrullus lanatus seed powder in continuous and discontinuous systems.

The objective of this study is to develop a low-cost biosorbent using residual seeds of the Citrullus lanatus fruit for the removal of cationic dyes. Physicochemical parameters such as pH, adsorbent mass, contact time, and temperature were evaluated for their effects on dye removal. The biosorbent is composed of lignin and cellulose, exhibiting a highly heterogeneous surface with randomly distributed cavities and bulges. The adsorption of both dyes was most effective at natural pH with a dosage of 0.8 g L-1. Equilibrium was reached within 120 min, regardless of concentration, indicating rapid kinetics. The Elovich model and pseudo-second-order kinetics were observed for crystal violet and basic fuchsin dye, respectively. The Langmuir model fitted well with the equilibrium data of both dyes. However, the increased temperature had a negative impact on dye adsorption. The biosorbent also demonstrated satisfactory performance (R = 43%) against a synthetic mixture of dyes and inorganic salts, with a small mass transfer zone. The adsorption capacities for crystal violet and basic fuchsin dye were 48.13 mg g-1 and 44.26 mg g-1, respectively. Thermodynamic studies confirmed an exothermic nature of adsorption. Overall, this low-cost biosorbent showed potential for the removal of dyes from aqueous solutions.

In this work, a novel biosorbent was developed using residual Citrullus lanatus fruit seeds that can efficiently remove cationic dyes from aqueous solutions. The biosorbent's composition includes lignin and cellulose, and its surface structure is highly heterogeneous, consisting of randomly distributed cavities and bulges. The biosorbent demonstrated a rapid and efficient adsorption capacity for both crystal violet and basic fuchsin, regardless of dye concentration. Moreover, the biosorbent was successfully employed in the treatment of a synthetic mixture containing several dyes and inorganic salts. Finally, the application of the biosorbent in continuous adsorption showed a low zone of mass transfer and high breakthrough time, indicating it to be an excellent material for fixed-bed operation. Overall, this study provides a low-cost and efficient alternative for the removal of dyes from aqueous solutions, with promising practical applications.

One step acid modification of the residual bark from Campomanesia guazumifolia using H2SO4 and application in the removal of 2,4-dichlorophenoxyacetic from aqueous solution.

The residual bark of the tree species Campomanesia guazumifolia was successfully modified with H2SO4 and applied to remove the toxic herbicide 2.4-dichlorophenoxyacetic (2.4-D) from aqueous solutions. The characterization techniques made it possible to observe that the material maintained its amorphous structure; however, a new FTIR band emerged, indicating the interaction of the lignocellulosic matrix with sulfuric acid. Micrographs showed that the material maintained its irregular shape; however, new spaces and cavities appeared after the acidic modification. Regardless of the herbicide concentration, the system tended to equilibrium after 120 min. Using the best statistical coefficients, the Elovich model was the one that best fitted the kinetic data. The temperature increase in the system negatively influenced the adsorption of 2.4-D, reaching a maximum capacity of 312.81 mg g-1 at 298 K. The equilibrium curves showed a better fit to the Tóth model. Thermodynamic parameters confirmed the exothermic nature of the system (ΔH0 = -59.86 kJ mol-1). As a residue obtained from urban pruning, the bark of Campomanesia guazumifolia treated with sulfuric acid is a promising and highly efficient alternative for removing the widely used and toxic 2.4-D herbicide from aqueous solutions.

Tribochemical Glass Ceramic Coating as a New Approach for Resin Adhesion to Zirconia.

PURPOSE: To investigate the effects of a novel tribochemical silica coating technique with powders made from feldspathic ceramic and leucite-based ceramic on the bond strength of zirconia to resin cement before and after aging. MATERIALS AND METHODS: Zirconia blocks were divided into 3 groups according to the material used for airborne-particle abrasion: 1) SP (control): silica-coated alumina particles; 2) FP: feldspathic ceramic powder; 3) LP: leucite glass-ceramic powder. After silanization, composite resin cylinders were cemented on the zirconia surface using a dual-curing resin cement. Prior to the shear bond strength (SBS) test, half of the samples (n = 15) were stored in distilled water for 24 h; the other half (n = 15) were submitted to aging (10,000 thermocycles of 5°C to 55°C; 150 days of water storage). The bond strength data were analyzed using two-way ANOVA and Tukey's test (α = 0.05). Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and x-ray diffraction analysis were performed. RESULTS: The initial bond strengths did not differ significantly between the groups (p = 0.053). However, after aging procedures, airborne-particle abrasion with feldspathic ceramic powder (FP) resulted in higher values of bond strength (p = 0.0001). SEM and EDS indicated that all the treatments promoted silica deposition on the Y-TZP surface ceramic. Airborne-particle abrasion with FP and LP induced a lower percentage of the monoclinic phase. CONCLUSION: Airborne abrasion with fine feldspathic ceramic particles is a novel tribochemical technique and appears to be suitable for improving the bond strength between zirconia and resin cements.

Comparison between Brazilian agro-wastes and activated carbon as adsorbents to remove Ni(II) from aqueous solutions.

This research was performed to find an alternative, low-cost, competitive, locally available and efficient adsorbent to treat nickel (Ni) containing effluents. For this purpose, several Brazilian agro-wastes like sugarcane bagasse (SCB), passion fruit wastes (PFW), orange peel (OP) and pineapple peel (PP) were compared with an activated carbon (AC). The adsorbents were characterized. Effects of fundamental factors affecting the adsorption were investigated using batch tests. Kinetic and equilibrium studies were performed using conventional models. It was verified that the adsorption was favored at pH of 6.0 for all agro-wastes, being dependent of the Ni speciation, point of zero charge and surface area of the adsorbents. The Ni removal percentage was in the following order: SCB > OP > AC > PFW > PP. From the kinetic viewpoint, the Elovich model was appropriate to fit the Ni adsorption onto SCB, while for the other adsorbents, the pseudo-first-order model was the most suitable. For all adsorbents, the Langmuir model was the more adequate to represent the equilibrium data, being the maximum adsorption capacities of 64.1 mg g(-1), 60.7 mg g(-1), 63.1 mg g(-1), 48.1 mg g(-1) and 64.3 mg g(-1) for SCB, PFW, OP, PP and AC, respectively. These results indicated that mainly SCB and OP can be used as alternative adsorbents to treat Ni containing effluents.

Degradation of Amaranth azo dye in water by heterogeneous photo-Fenton process using FeWO4 catalyst prepared by microwave irradiation.

FeWO4 particles were synthesized by a simple, rapid and facile microwave technique and their catalytic properties in heterogeneous photo-Fenton reaction were evaluated. This material was employed in the degradation of Amaranth azo dye. Individual and interactive effects of operational parameters such as pH, dye concentration and H2O2 dosage on the decolorization efficiency of Amaranth dye were evaluated by 2(3) central composite design. According to characterization techniques, a porous material and a well-crystallized phase of FeWO4 oxide were obtained. Regarding the photo-Fenton reaction assays, up to 97% color and 58% organic carbon removal were achieved in the best experimental conditions. In addition, the photo-Fenton process maintained treatment efficiency over five catalyst reuse cycles to indicate the durability of the FeWO4 catalyst. In summary, the results reveal that the synthesized FeWO4 material is a promising catalyst for wastewater treatment by heterogeneous photo-Fenton process.

Oil removal from produced water by conjugation of flotation and photo-Fenton processes.

The present work investigates the conjugation of flotation and photo-Fenton techniques on oil removal performance from oilfield produced water. The experiments were conducted in a column flotation and annular lamp reactor for induced air flotation and photodegradation steps, respectively. A nonionic surfactant was used as a flotation agent. The flotation experimental data were analyzed in terms of a first-order kinetic rate model. Two experimental designs were employed to evaluate the oil removal efficiency: fractional experimental design and central composite rotational design (CCRD). Overall oil removal of 99% was reached in the optimum experimental condition after 10 min of flotation followed by 45 min of photo-Fenton. The results of the conjugation of induced air flotation and photo-Fenton processes allowed meeting the wastewater limits established by the legislations for disposal.

Carbon nanotubes as supports for inulinase immobilization.

The commercial inulinase obtained from Aspergillus niger was non-covalently immobilized on multiwalled carbon nanotubes (MWNT-COOH). The immobilization conditions for the carbon nanotubes were defined by the central composite rotational design (CCRD). The effects of enzyme concentration (0.8%-1.7% v/v) and adsorbent:adsorbate ratio (1:460-1:175) on the enzyme immobilization were studied. The adsorbent:adsorbate ratio variable has positive effect and the enzyme concentration has a negative effect on the inulinase immobilization (U/g) response at the 90% significance level. These results show that the lower the enzyme concentration and the higher the adsorbent:adsorbate ratio, better is the immobilization. According to the results, it is possible to observe that the carbon nanotubes present an effective inulinase adsorption. Fast adsorption in about six minutes and a loading capacity of 51,047 U/g support using a 1.3% (v/v) inulinase concentration and a 1:460 adsorbent:adsorbate ratio was observed. The effects of temperature on the immobilized enzyme activity were evaluated, showing better activity at 50 °C. The immobilized enzyme maintained 100% of its activity during five weeks at room temperature. The immobilization strategy with MWNT-COOH was defined by the experimental design, showing that inulinase immobilization is a promising biotechnological application of carbon nanotubes.

Removal of hazardous pharmaceutical dyes by adsorption onto papaya seeds.

Papaya (Carica papaya L.) seeds were used as adsorbent to remove toxic pharmaceutical dyes (tartrazine and amaranth) from aqueous solutions, in order to extend application range. The effects of pH, initial dye concentration, contact time and temperature were investigated. The kinetic data were evaluated by the pseudo first-order, pseudo second-order and Elovich models. The equilibrium was evaluated by the Langmuir, Freundlich and Temkin isotherm models. It was found that adsorption favored a pH of 2.5, temperature of 298 K and equilibrium was attained at 180-200 min. The adsorption kinetics followed the pseudo second-order model, and the equilibrium was well represented by the Langmuir model. The maximum adsorption capacities were 51.0 and 37.4 mg g(-1) for tartrazine and amaranth, respectively. These results revealed that papaya seeds can be used as an alternative adsorbent to remove pharmaceutical dyes from aqueous solutions.

Application of artificial neural network for modeling of phenol mineralization by photo-Fenton process using a multi-lamp reactor.

An artificial neural network (ANN) was implemented for modeling phenol mineralization in aqueous solution using the photo-Fenton process. The experiments were conducted in a photochemical multi-lamp reactor equipped with twelve fluorescent black light lamps (40 W each) irradiating UV light. A three-layer neural network was optimized in order to model the behavior of the process. The concentrations of ferrous ions and hydrogen peroxide, and the reaction time were introduced as inputs of the network and the efficiency of phenol mineralization was expressed in terms of dissolved organic carbon (DOC) as an output. Both concentrations of Fe(2+) and H2O2 were shown to be significant parameters on the phenol mineralization process. The ANN model provided the best result through the application of six neurons in the hidden layer, resulting in a high determination coefficient. The ANN model was shown to be efficient in the simulation of phenol mineralization through the photo-Fenton process using a multi-lamp reactor.

Photo-Fenton degradation of phenol, 2,4-dichlorophenoxyacetic acid and 2,4-dichlorophenol mixture in saline solution using a falling-film solar reactor.

In this work, a saline aqueous solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a falling-film solar reactor. The influence of the parameters such as initial pH (5-7), initial concentration of Fe2+ (1-2.5mM) and rate of H202 addition (1.87-3.74mmol min-1) was investigated. The efficiency of photodegradation was determined from the removal of dissolved organic carbon (DOC), described by the species degradation of phenol, 2,4-D and 2,4-DCP. Response surface methodology was employed to assess the effects of the variables investigated, i.e. [Fe2+], [H202] and pH, in the photo-Fenton process with solar irradiation. The results reveal that the variables' initial concentration of Fe2+ and H202 presents predominant effect on pollutants' degradation in terms of DOC removal, while pH showed no influence. Under the most adequate experimental conditions, about 85% DOC removal was obtained in 180 min by using a reaction system employed here, and total removal of phenol, 2,4- and 2,4-DCP mixture in about 30min.

Photodegradation of non-ionic surfactant with different ethoxy groups in aqueous effluents by the photo-Fenton process.

The photo-Fenton process was applied to degrade non-ionic surfactants with different numbers of ethoxy groups, seven (E7), ten (E10) and twenty-three (E23). The effects of H2O2 concentration, Fe(II) concentration and number of ethoxy groups on the mineralization of surfactants were investigated. The response surface methodology (RSM) was applied to determine optimal concentrations of Fenton's reagents for each surfactant. The efficiency of the photo-Fenton process reached 95% for all surfactants studied at 45 min in optimal conditions determined in this work. The analysis of results showed that the efficiency depends upon the number of ethoxy groups in the surfactant. The increase in ethoxy groups favoured the mineralization of surfactants. The analysis of variance (ANOVA) was applied, and according to the F-test the models for the mineralization of surfactants were considered significant and predictable. The photo-Fenton process has proven to be feasible for the degradation of ethoxylated surfactants in aqueous solution.

Iron-bearing mining reject as an alternative and effective catalyst for photo-Fenton oxidation of phenol in water.

In this work, iron-bearing mining reject was employed as an alternative and potential low-cost catalyst to degrade phenol in water by photo-Fenton strategy. Various techniques, including SEM-EDS, BET, FTIR, and XRD, were applied to evaluate the material's properties. Process parameters such as hydrogen peroxide concentration, catalyst dosage, and pH were studied to determine the optimum reaction conditions ([catalyst] = 0.75 g L-1, [H2O2] = 7.5 mM, and pH = 3). Phenol degradation and mineralization efficiencies at 180 and 300 min were 96.5 and 78%, respectively. These satisfactory results can be associated with the iron amount present in the waste sample. Furthermore, the material showed high catalytic activity and negligible iron leaching even after the fourth reuse cycle. The degradation behavior of phenol in water was well represented by a kinetic model based on the Fermi function. The iron-bearing mining reject can be considered a potential photo-Fenton catalyst for phenol degradation in wastewater.

Adsorption of leather dye onto activated carbon prepared from bottle gourd: equilibrium, kinetic and mechanism studies.

Activated carbon prepared from bottle gourd has been used as adsorbent for removal of leather dye (Direct Black 38) from aqueous solution. The activated carbon obtained showed a mesoporous texture, with surface area of 556.16 m(2) g(-1), and a surface free of organic functional groups. The initial dye concentration, contact time and pH significantly influenced the adsorption capacity. In the acid region (pH 2.5) the adsorption of dye was more favorable. The adsorption equilibrium was attained after 60 min. Equilibrium data were analyzed by the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The equilibrium data were best described by the Langmuir isotherm, with maximum adsorption capacity of 94.9 mg g(-1). Adsorption kinetic data were fitted using the pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The adsorption kinetic was best described by the second-order kinetic equation. The adsorption process was controlled by both external mass transfer and intraparticle diffusion. Activated carbon prepared from bottle gourd was shown to be a promising material for adsorption of Direct Black 38 from aqueous solution.

Use of papaya seeds as a biosorbent of methylene blue from aqueous solution.

In this study papaya seeds were used to remove methylene blue dye from aqueous solution. Papaya seeds were characterized as possessing a macro/mesoporous texture and large pore size. Studies were carried out in batches to evaluate the effect of contact time and pH (2-12) on the removal of dye. It was observed that the adsorption of dye was better in the basic region (pH 12). The equilibrium data were analyzed using Langmuir, Freundlich, Dubinin-Raduschkevich, Tempkin, Jovanovich, Redlich-Peterson, Sips, Toth and Radke-Prausnitz isotherms. The equilibrium data were best described by the Langmuir isotherm with a maximum adsorption capacity of 637.29 mg g(-1). Adsorption kinetic data were fitted using the pseudo-first-order and pseudo-second-order model. The adsorption kinetic is very fast and was best described by the pseudo-second-order model.

CuO/ZnO coupled oxide films obtained by the electrodeposition technique and their photocatalytic activity in phenol degradation under solar irradiation.

CuO/ZnO coupled oxide films were electrodeposited onto an aluminum substrate and tested as photocatalysts in degradation of phenol molecules in aqueous solution under sunlight. The obtained films were characterized by X-ray diffraction, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The results showed that the photocatalytic activity of films was significant, especially to coupled oxide film with a CuO/ZnO ratio equal to 0.697, which presented about 70% degradation of the aromatic molecules and 42% of total organic carbon (TOC) removal at 300 min under solar irradiation. Therefore, this work highlights the potential application of CuO/ZnO coupled oxide films obtained by electrodeposition onto aluminum substrate in the field of photocatalysis.

Activated carbon prepared from yerba mate used as a novel adsorbent for removal of tannery dye from aqueous solution.

Activated carbon prepared from yerba mate (Ilex paraguariensis) was used as adsorbent for the removal of tannery dye from aqueous solution. The activated carbon was characterized, and it showed a mesoporous texture, with surface area of 537.4 m2 g(-1). The initial dye concentration, contact time and pH influenced the adsorption capacity. The equilibrium data were in good agreement with both Langmuir and Freundlich isotherms. The adsorption kinetics of the tannery dye on activated carbon prepared from yerba mate followed a pseudo-second-order model. The adsorption process was found to be controlled by both external mass-transfer and intraparticle diffusion, but the external diffusion was the dominating process. This work highlights the potential application of activated carbon produced from yerba mate in the field of adsorption.

Augmented degradation of dyed organic pollutant using Fe2O3 supported on char formed from poultry slaughterhouse waste.

In this work, a novel support for an iron-based catalyst was prepared and employed for Ponceau 4R degradation by photo-Fenton reaction. To this, poultry waste was used for producing char, which was subsequently used to prepare the Fe2O3/Char composite. Process parameters, including catalyst dosage, pH, and hydrogen peroxide concentration, were investigated. The characterization analysis indicated that the textural properties of the composite were improved after impregnation with Fe2O3. The composite exhibited excellent catalytic activity, achieving a decolorization efficiency of 97% at 45 min and 81.06% organic carbon removal at 300 min. In addition, the material showed acceptable performance after four consecutive cycles. Furthermore, a scavenger test was performed to investigate the major reactive species involved in the Ponceau 4R oxidation, and a plausible mechanism for the respective reaction was projected. Therefore, the results of this research demonstrate that this material can be used as a potential catalyst for the abatement of dyed molecules from wastewater.

Remarkable photocatalytic performances towards pollutant degradation under sunlight and enhanced electrochemical properties of TiO2/polymer nanohybrids.

In this work, TiO2-based nanocomposites containing polyaniline (PANI), poly(1-naphthylamine) (PNA), and polyindole (PIN) were synthesized by effective and simple routes and posteriorly employed as photocatalysts and supercapacitors. Characterization techniques such as XRD, FTIR, FESEM, UV, and PL were employed to investigate the structural, morphological, and optical properties of materials. XRD analysis confirmed the successful formation of TiO2 and TiO2/polymer nanocomposites. PANI, PNA, and PIN polymers were well distributed on the surface of TiO2 nanoparticles and were investigated/explored from the FESEM analysis. The visible light absorption and the recombination rate of photogenerated charge carriers were confirmed by the UV-Vis and PL analysis. The photocatalytic properties of the nanocomposites were investigated towards malachite green (MG) dye degradation under sunlight. The dye degradation efficiency followed the order TiO2/PNA > TiO2/PANI > TiO2 > TiO2/PIN. The higher efficiency of TiO2/PNA can be associated with its smaller bandgap energy compared to the other materials. Electrochemical properties of materials were also examined by cyclic voltammetry and galvanostatic charge-discharge measurements using a three-electrode experiment setup in an aqueous electrolyte. TiO2/PNA nanocomposite showed higher supercapacitor behavior compared to the other materials due to higher electrical conductivity of PNA and redox potential of TiO2 (pseudocapacitance).

Application of green-synthesized cadmium oxide nanofibers and cadmium oxide/graphene nanosheet nanocomposites as alternative and efficient photocatalysts for methylene blue removal from aqueous matrix.

For the first time, cadmium oxide (CdO) nanofibers (NFs) and graphene nanosheet (GNS)-doped CdO nanocomposites (NCs) have been synthesized by a simple green route using green tea (Camellia sinensis) extract, for subsequent application as photocatalysts for methylene blue (MB) removal from an aqueous matrix. In addition, the materials were tested as working electrodes for supercapacitors. The prepared samples were analyzed by FESEM, UV-Vis spectroscopy, FTIR, and X-ray diffraction (XRD). FESEM revealed that the obtained NPs and NCs show fiber-shaped nanostructure. FTIR confirmed the presence of biomolecules on CdO and carbon compounds on CdO/GNS, while XRD exhibited the cubic crystalline structure of obtained NPs and NCs. The Rietveld refinement using XRD data was performed to ascertain the crystallographic characteristics of the produced samples and look into lattice imperfections. UV-Vis spectroscopy evaluated the optical bandgap energies of CdO and CdO/GNS NCs. The CdO/GNS NCs demonstrated a fast cleavage of the dye molecule under UV irradiation, resulting in 97% removal in 120 min. In addition, CdO/GNS NCs showed remarkable chemical stability as an electrode material, with a high specific capacitance of 231 F g-1 at a scan rate of 25 mV s-1. These observed NCs characteristics are higher when compared to pristine CdO NPs. Finally, we found that the investigated NCs showed enhanced multifunctional properties, such as photocatalytic and supercapacitor characteristics, which can be useful in practical applications.

Applying bottom ash as an alternative Fenton catalyst for effective removal of phenol from aqueous environment.

In this study, coal bottom ash from a thermoelectric plant was tested as an alternative Fenton catalyst for phenol degradation in water. The effect of operating parameters such as initial pH, catalyst dosage and H2O2 concentration were evaluated. The characterization results indicated that the material has a mesoporous structure, with active species (Fe) well distributed on its surface. Under the optimal reaction conditions (6 mM H2O2, 1 g L-1 of catalyst and pH = 3), 98.7% phenol degradation efficiency was achieved in 60 min, as well as 71.6% TOC removal after 150 min. Hydroxyl radical was identified as the main oxidizing agent involved on the cleavage of the phenol molecule. After four consecutive reuse cycles, phenol degradation efficiency was around 80%, indicating good reusability and stability of the catalyst. Therefore, the obtained results demonstrated that the bottom ash presents remarkable activity for application in the Fenton reaction towards phenol degradation.