Optimisation of decolourisation and degradation of Reactive Black 5 dye under electro-Fenton process using Fe alginate gel beads

The aim of this work was to improve the ability of the electro-Fenton process using Fe alginate gel beads for the remediation of wastewater contaminated with synthetic dyes and using a model diazo dye such as Reactive Black 5 (RB5). Batch experiments were conducted to study the effects of main parameters, such as voltage, pH and iron concentration. Dye decolourisation, reduction of chemical oxygen demand (COD) and energy consumption were studied. Central composite face-centred experimental design matrix and response surface methodology were applied to design the experiments and to evaluate the interactive effects of the three studied parameters. A total of 20 experimental runs were set, and the kinetic data were analysed using first-order and second-order models. In all cases, the experimental data were fitted to the empirical second-order model with a suitable degree for the maximum decolourisation of RB5, COD reduction and energy consumption by electro-Fenton–Fe alginate gel beads treatment. Working with the obtained empirical model, the optimisation of the process was carried out. The second-order polynomial regression model suggests that the optimum conditions for attaining maximum decolourisation, COD reduction and energy consumption are voltage, 5.69 V; pH 2.24 and iron concentration, 2.68 mM. Moreover, the fixation of iron on alginate beads suggests that the degradation process can be developed under this electro-Fenton process in repeated batches and in a continuous mode.     

Using iron-loaded sepiolite obtained by adsorption as a catalyst in the electro-Fenton oxidation of Reactive Black 5

This study explores the possibility of using iron-loaded sepiolite, obtained by recovering iron from polluted water, as a catalyst in the electro-Fenton oxidation of organic pollutants in textile effluents. The removal of iron ions from aqueous solution by adsorption on sepiolite was studied in batch tests at iron concentrations between 100 and 1,000 ppm. Electro-Fenton experiments were carried out in an electrochemical cell with a working volume of 0.15 L, an air flow of 1 L/min, and 3 g of iron-loaded sepiolite. An electric field was applied using a boron-doped diamond anode and a graphite sheet cathode connected to a direct current power supply with a constant potential drop. Reactive Black 5 (100 mg/L) was selected as the model dye. The adsorption isotherms proved the ability of the used adsorbent. The removal of the iron ion by adsorption on sepiolite was in the range of 80–100 % for the studied concentration range. The Langmuir and Freundlich isotherms were found to be applicable in terms of the relatively high regression values. Iron-loaded sepiolite could be used as an effective heterogeneous catalyst for the degradation of organic dyes in the electro-Fenton process. Successive batch processes were performed at optimal working conditions (5 V and pH 2). The results indicate the suitability of the proposed combined process, adsorption to iron remediation followed by the application of the obtained iron-loaded sepiolite to the electro-Fenton technique, to oxidize polluted effluents.     

Photocatalytic degradation of dyes in aqueous solution operating in a fluidised bed reactor.

This work reports a preliminary design of a new photochemical reactor and its application to photochemical degradation of two dyes, Crystal Violet and Azure B, operating in both batch and continuous processes. A novel kind of photocatalyst, consisting of ZnO immobilised in alginate gel beads, which is able to photodegrade organic dyes effectively, has been employed in the present study. When this photocatalyst, at a concentration of 1 g of ZnO per litre of alginate gel at 3%, was employed in batch process, almost total decolourisation of Crystal Violet in reaction times lower than 120 min was observed. Operating in continuous process at different residence times, it was possible to achieve a total decolourisation of both Crystal Violet and Azure B. Moreover, the total organic carbon content (TOC) was reduced to 90% in the former and to 52% in the latter. These results indicated that the photoreactor developed in the present work was able to degrade effectively dyes of different structures, revealing the non-specificity of the system.     

Treatment of phenol-containing wastewater by photoelectro-Fenton method using supported nanoscale zero-valent iron

This study presents the degradation of phenol by the photoelectro-Fenton method using nano zero-valent iron (nZVI) immobilized in polyvinyl alcohol–alginate beads. The effect of nZVI loading, H₂O₂ concentration, pH, and initial phenol concentration on phenol degradation and chemical oxygen demand reduction was studied. The scanning electron microscope images of the nZVI beads were used to analyze their morphology, and their diameters were in the range of 500–600 μm. The concentration of nZVI in the beads was varied from 0.1 to 0.6 g/L. Fe²⁺ leakage of 1 and 3 % was observed with 0.5 and 0.6 g/L of nZVI, respectively, and the observed beads' fracture frequency was 2 %, which confirmed the stability of the beads. The optimum operating conditions that arrived for better degradation were 0.5 g/L of nZVI, pH 6.2, and 400 mg H₂O₂/L. The treatment of effluent by this method increased the biodegradability index of the effluent, and the degradation data were found to follow pseudo first-order kinetics.     

Biodegradation of quinoline by gel immobilized Burkholderia sp

Burkholderia sp, a gram-negative, rod-shaped, aerobe, capable of degrading quinoline was immobilized in calcium alginate gel beads and used for degradation of quinoline in aqueous solution in the reactor. The optimal conditions for immobilization of the microorganism, such as alginate concentration, calcium ion concentration, initial cell loading, hardening time and bead size, were determined with a view to improving the quinoline degradation rate. The characteristics of quinoline degradation by immobilized microbial cells were investigated. The repeated use of immobilized cells for quinoline degradation was performed and the results revealed that the bioactivity of immobilized cells was stable over 100 h in the repeated batch cultivation for quinoline degradation.     

Alginate immobilized enrichment culture for atrazine degradation in soil and water system

An atrazine degrading enrichment culture, a consortium of bacteria of genus Bacillus along with Pseudomonas and Burkholderia, was immobilized in sodium alginate and was used to study atrazine degradation in mineral salts medium (MSM), soil and wastewater effluent. Sodium alginate immobilized consortium, when stored at room temperature (24 ± 5°C), was effective in degrading atrazine in MSM up to 90 days of storage. The survival of bacteria in alginate beads, based on colony formation unit (CFU) counts, suggested survival up to 90 days and population counts decreased to 1/5^th on 120 days. Comparison of atrazine degrading ability of the freely suspended enrichment culture and immobilized culture suggested that the immobilized culture took longer time for complete degradation of atrazine as a lag phase of 2 days was observed in the MSM inoculated with alginate immobilized culture. The free cells resulted in complete degradation of atrazine within 6 days, while immobilized cells took 10 days for 100% atrazine degradation. Further, immobilized cultures were able to degrade atrazine in soil and wastewater effluent. Alginate beads were stable and effective in degrading atrazine till 3rd transfer and disintegrated thereafter. The study suggested that immobilized enrichment culture, due to its better storage and application, can be used to degrade atrazine in soil water system.     

Treatment of Basic Red 29 dye solution using iron-aluminum electrode pairs by electrocoagulation and electro-Fenton methods

The aim of this study is the treatment of Basic Red 29 (BR29) dye solution using hybrid iron-aluminum electrodes by electrocoagulation and electro-Fenton methods. The effect of current density, initial pH, supporting electrolyte, H₂O₂, and initial dye concentration on dye removal efficiency was investigated, and the best experimental conditions were obtained. Time-coarse variation of UV-Vis spectra and toxicity and chemical oxygen demand (COD) removal were also examined at the best experimental conditions. Both systems were found very successful for the removal of BR29 dye. The removal efficiency of >95 % for BR29 dye solution was reached easily in a short time. At the best experimental conditions, for the initial BR29 concentration of 100 mg/L, >95 % BR29 dye and 71.43 % COD removal were obtained after 20 and 40 min of electrolysis, respectively. Additionally, toxicity results for electro-Fenton treatment of 100 mg/L BR29 were also very promising. According to the results obtained, although electro-Fenton is more effective, both systems can be used successfully to treat textile wastewater including dyes.     

Adsorption of Cu and Mn on covalently cross-linked alginate gel beads

The covalently cross-linked alginate gel beads were prepared by the reactions of Ca(2+)-doped alginate gel beads, which were formed by spraying a viscous alginate solution into a calcium chloride solution, with cyanogen bromide and following 1,6-diaminohexane. The cross-linking of alginate matrix decreased the mean bead diameter by about 30% and made the beads durable in some extent under alkaline conditions. The adsorption of metal ions on the covalently cross-linked alginate gel beads was rapid and reached at equilibrium within 30 min at 25 degrees C. Adsorption isotherms of Cu(II), Mn(II), and Ca2+ on the beads possessed a stepwise shape, which was firstly determined by Rorrer et al. [Ind. Eng. Chem. Res. 32 (1993) 2170] for cross-linked chitosan gel beads and explained by a pore-blockage mechanism. Higher selectivity was determined against Cu(II) over Mn(II) and Ca2+, especially at a low concentration region. These metal adsorption profiles for the covalently cross-linked alginate gel beads was almost the same as those for the un-cross-linked beads, indicating that the cross-linking reactions were performed without interfering the adsorption characteristics of alginate gel beads.     

Simultaneous removal of nitrate and pentachlorophenol from simulated groundwater using a biodenitrification reactor packed with corncob

Both nitrate and pentachlorophenol (PCP) are familiar pollutants in aqueous environment. This research is focused on the simultaneous removal of nitrate and PCP from simulated contaminated groundwater using a laboratory-scale denitrification reactor packed with corncob as both carbon source and biofilm support. The reactor could be started up readily, and the removal efficiencies of nitrate and PCP reached up to approximately 98 % and 40–45 % when their initial concentrations were 50 mg N/L and 5 mg/L, respectively, after 15-day continuous operation at 10 h of hydraulic retention time (HRT) and 25 °C. Approximately 91 % of PCP removal efficiency was achieved, with 2.47 mg/L of chloride ion release at 24 h of HRT. Eighty-two percent of chlorine in PCP removed was ionized. The productions of 3-chlorophenol and phenol and chloride ion release indicate that the reductive dechlorination reaction is a major degradation pathway of PCP under the experimental conditions.     

Immobilized Fe (III)-doped titanium dioxide for photodegradation of dissolved organic compounds in water

Photocatalytic degradation of dissolved organic carbon (DOC) by utilizing Fe(III)-doped TiO₂ at the visible radiation range is hereby reported. The photocatalyst was immobilized on sintered glass frits with the coating done by wet method, calcinated at 500 °C and then applied in a photodegradation reactor. The addition of a transition metal dopant, Fe(III), initiated the red shift which was confirmed by UV–Vis spectroscopy, and the photocatalyst was activated by visible radiation. X-ray diffraction patterns showed that Fe(III) doping had an effect on the crystallinity of the photocatalysts. Mixtures of DOC and associated coloured solutions were degraded in first-order kinetics, showing that the degradation process was not dependent on intermediates or other species in solution. A reactor with a catalyst coating area of 12.57 cm² was able to degrade 0.623 mg of the dissolved material per minute. Exposure of the reactor to hostile acidic conditions and repeated use did not compromise its efficiency. It was observed that the reactor regenerates itself in the presence of visible light, and therefore, it can be re-used for more than 100 runs before the performance dropped to <95 %. The results obtained indicate that the photocatalyst reactor has a great potential of application for use in tandem with biosorbent cartridges to complement water purification methods for domestic consumption.     

Recent updates on electrochemical degradation of bio-refractory organic pollutants using BDD anode: a mini review

Boron-doped diamond (BDD) is playing an important role in environmental electrochemistry and has been successfully applied to the degradation of various bio-refractory organic pollutants. However, the review concerning recent progress in this research area is still very limited. This mini-review updated recent advances on the removal of three kinds of bio-refractory wastewaters including pharmaceuticals, pesticides, and dyes using BDD electrode. It summarized the important parameters in three electrochemical oxidation processes, i.e., anodic oxidation (AO), electro-Fenton (EF), and photoelectro-Fenton (PEF) and compared their different degradation mechanisms and behaviors. As an attractive improvement of PEF, solar photoelectro-Fenton using sunlight as UV/vis source presented cost-effectiveness, in which the energy consumption for enrofloxacin removal was 0.246 kWh/(g TOC), which was much lower than that of 0.743 and 0.467 kWh/(g TOC) by AO and EF under similar conditions. Finally the existing problems and future prospects in research were suggested.     

Model reactor for photocatalytic degradation of persistent chemicals in ponds and waste water

A laboratory scale flow-through model reactor for the degradation of persistent chemicals using titanium dioxide (TiO₂) as photocatalyst immobilized on glass beads is presented. In the test system with a volume of 18 L contaminated water is pumped to the upper part of the floating reactor and flows over the coated beads which are exposed to UV-radiation. The degradation of two dyes of different persistance was investigated. Primary degradation of methylene blue did not fit a first order kinetic due to coincident adsorption onto the photocatalyst and direct photolysis, resulting in a half-life of 6 h. A filtrate of a green algae suspension accelerated the colour removal. In contrast, reactive red 2 was degraded only by photocatalysis; neither adsorption nor direct photolysis led to a colour removal. The course of primary degradation followed a first order kinetic with a half-life of 18 h and a rate constant of 0.04 h⁻¹. Analysis of the degradation products indicated mineralization by detection of NO₂⁻ and NO₃⁻, accompanied by a decrease of pH and an increase of conductivity. A successful adaptation of the model reactor (scale 1:10) to dimensions required for surface waters and waste water treatment plants would be a costefficient and environmentally sustainable application of photocatalysis for the treatment of industrially polluted water and could be of relevance for third world contries, particularly those favoured by high solar radiation.     

Efficient degradation of rhodamine B using modified graphite felt gas diffusion electrode by electro-Fenton process

The electro-Fenton (EF) process treatment of 0.1-M (rhodamine B) RhB solution was studied with different graphite cathode materials, and graphite felt (GF) was selected as a promising material in further investigation. Then, the degradation performances of gas diffusion electrode (GDE) and graphite felt (GF) were compared, and GDE was confirmed to be more efficient in RhB removal. The operational parameters such as Fe²⁺ dosage and current density were optimized, and comparison among different modified methods—polytetrafluoroethylene-carbon black (PTFE-CB), polytetrafluoroethylene-carbon nanotube (PTFE-CNT), electrodeposition-CB, and electrodeposition-CNT—showed 98.49 % RhB removal by PTFE-CB-modified cathode in 0.05 M Na₂SO₄ at a current density of 50 A/m² and an air flow rate of 1 L/min after 20 min. Meanwhile, after cathode modified by PTFE-CB, the mineralization efficiency and mineralization current efficiency performed absolutely better than the pristine one. Cyclic voltammograms, SEM images, contact angles, and BET surface area were carried out to demonstrate stronger current responses and higher hydrophilicity of GF after modified. The value of biochemical oxygen demand/chemical oxygen demand (BOD₅/COD) increased from 0.049 to 0.331 after 90-min treatment, suggesting the solution was biodegradable, and the modified cathode was confirmed to be stable after ten circle runs. Finally, a proposed degradation pathway of RhB was put forward.     

Degradation of propyl paraben by activated persulfate using iron-containing magnetic carbon xerogels: investigation of water matrix and process synergy effects

An advanced oxidation process comprising an iron-containing magnetic carbon xerogel (CX/Fe) and persulfate was tested for the degradation of propyl paraben (PP), a contaminant of emerging concern, in various water matrices. Moreover, the effect of 20 kHz ultrasound or light irradiation on process performance was evaluated. The pseudo-first order degradation rate of PP was found to increase with increasing SPS concentration (25–500 mg/L) and decreasing PP concentration (1690–420 μg/L) and solution pH (9–3). Furthermore, the effect of water matrix on kinetics was detrimental depending on the complexity (i.e., wastewater, river water, bottled water) and the concentration of matrix constituents (i.e., humic acid, chloride, bicarbonate). The simultaneous use of CX/Fe and ultrasound as persulfate activators resulted in a synergistic effect, with the level of synergy (between 35 and 50%) depending on the water matrix. Conversely, coupling CX/Fe with simulated solar or UVA irradiation resulted in a cumulative effect in experiments performed in ultrapure water.     

Study of the performance of a cylindrical flow-through electro-Fenton reactor using different arrangements of carbon felt electrodes: effect of key operating parameters

Environmental Science and Pollution Research - In this work, a cylindrical flow-through electro-Fenton reactor containing graphite felt electrodes and an Fe(II) loaded resin was evaluated for the...     

Electro-Fenton pretreatment for the improvement of tylosin biodegradability

The feasibility of an electro-Fenton process to treat tylosin (TYL), a non-biodegradable antibiotic, was examined in a discontinuous electrochemical cell with divided cathodic and anodic compartments. Only 15 min electrolysis was needed for total tylosin degradation using a carbon felt cathode and a platinum anode; while 6 h electrolysis was needed to achieve high oxidation and mineralization yields, 96 and 88 % respectively. Biodegradability improvement was shown since BOD₅/COD increased from 0 initially to 0.6 after 6 h electrolysis (for 100 mg L^?1 initial TYL). With the aim of combining electro-Fenton with a biological treatment, an oxidation time in the range 2 to 4 h has been however considered. Results of AOS (average oxidation state) and COD/TOC suggested that the pretreatment could be stopped after 2 h rather than 4 h; while in the same time, the increase of biodegradability between 2 and 4 h suggested that this latter duration seemed more appropriate. In order to conclude, biological cultures have been therefore carried out for various electrolysis times. TYL solutions electrolyzed during 2 and 4 h were then treated with activated sludge during 25 days, showing 57 and 67 % total organic carbon (TOC) removal, respectively, namely 77 and 88 % overall TOC removal if both processes were considered. Activated sludge cultures appeared, therefore, in agreement with the assessment made from the analysis of physico-chemical parameters (AOS and COD/TOC), since the gain in terms of mineralization expected from increasing electrolysis duration appeared too low to balance the additional energy consumption.     

Efficient removal of insecticide “imidacloprid” from water by electrochemical advanced oxidation processes

The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k _abs(ICP)?=?1.23?×?10⁹ L mol^?1 s^?1. The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94 % total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71 %. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl^?, NO₃ ^?, and NH₄ ⁺.     

Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Coal fly ash as adsorptive material for treatment of a real textile effluent: operating parameters and treatment efficiency

The experimental results performed after the application of one single-stage treatment by sorption onto coal fly ash are evaluated in order to decolorize a real textile effluent of a private company specializing in manufacturing of cotton fabrics (i.e., sorption performance applied for a real textile effluent collected after the fabric dyeing, rinsing, and final finishing steps). The experiments are focused on studying the effect of initial textile effluent pH, adsorbent dose, temperature and adsorption time, considered as operating parameters of sorption process for high pollutant removals (e.g., organic pollutants as dyes, phenols, polymeric, and degradation compounds), and decoloration. The results indicate high values of decoloration degree (55.42–83.00 %) and COD removal (44.44–61.11 %) when it is worked at pH ≤2 with coal ash dose of 12–40 g/L, temperature higher than 20–25 °C, and continuous static operating regime (with an initial agitation step of 3–5 min). The treated textile effluent fulfills the quality demand, and is recyclable, inside reused or discharged after a stage of neutralization (standard pH of 6.5–8.5 for all textile effluent discharges). Also, the final effluent is able to follow the common path to the central biological treatment plant (i.e., a centralized treatment plant for all companies acting in the industrial site area with mechanical–biological steps for wastewater treatment) or may be directly discharged in the nearly watercourse.     

Isovaleraldehyde elimination by UV/TiO2 photocatalysis: comparative study of the process at different reactors configurations and scales

A proposal for scaling-up the photocatalytic reactors is described and applied to the coated catalytic walls with a thin layer of titanium dioxide under the near ultraviolet (UV) irradiation. In this context, the photocatalytic degradation of isovaleraldehyde in gas phase is studied. In fact, the removal capacity is compared at different continuous reactors: a photocatalytic cylindrical reactor, planar reactor, and pilot unit. Results show that laboratory results can be useful for reactor design and scale-up. The flowrate increases lead to the removal capacity increases also. For example, with pilot unit, when flowrate extends four times, the degradation rate varies from 0.14 to 0.38 g h^?1 m_cat ^?2. The influence of UV intensity is also studied. When this parameter increases, zboth degradation rate and overall mineralization are enhanced. Moreover, the effects of inlet concentration, flowrate, geometries, and size of reactors on the removal capacity are also studied.