DSA electrochemical treatment of olive mill wastewater on Ti/RuO<Subscript>2</Subscript> anode

The electrochemical oxidation of olive mill wastewater (OMW) over a Ti/RuO₂ anode was studied by means of cyclic voltammetry and bulk electrolysis and compared with previous results over a Ti/IrO₂ anode. Experiments were conducted at 300–1,220 mg L⁻¹ initial chemical oxygen demand (COD) concentrations, 0.05–1.35 V versus SHE and 1.39–1.48 V versus SHE potential windows, 15–50 mA cm⁻² current densities, 0–20 mM NaCl, Na₂SO₄, or FeCl₃ concentrations, 80 °C temperature, and acidic conditions. Partial and total oxidation reactions occur with the overall rate being near first-order kinetics with respect to COD. Oxidation at 28 Ah L⁻¹ and 50 mA cm⁻² leads to quite high color and phenols removal (86 and 84%, respectively), elimination of ecotoxicity, and a satisfactory COD and total organic carbon reduction (52 and 38%, respectively). Similar performance can be achieved at the same charge (28 Ah L⁻¹) using lower current densities (15 mA cm⁻²) but in the presence of various salts. For example, COD removal is less than 7% at 28 Ah L⁻¹ in a salt-free sample, while addition of 20 mM NaCl results in 54% COD reduction. Decolorization of OMW using Ti/RuO₂ anode seems to be independent of the presence of salts in contrast with Ti/IrO₂ where addition of NaCl has a beneficial effect on decolorization.     

Treatment of olive mill wastewater by the combination of ultrafiltration and bipolar electrochemical reactor processes

The main purpose of this study was to investigate the removal of the chemical oxygen demand (COD) from olive mill wastewater (OMW) by the combination of ultrafiltration with electrocoagulation process. Ultrafiltration process equipped with CERAVER membrane was used as pre-treatment for electrochemical process. The obtained permeate from the ultrafiltration process allowed COD removal efficiency of about 96% from OMW. Obtained permeate with an average COD of about 1.1 g dm⁻³ was treated by electrochemical reactor equipped with a reactor with bipolar iron plate electrodes. The effect of the experimental parameters such as current density, pH, surface electrode/reactor volume ratio and NaCl concentration on COD removal was assessed. The results showed that the optimum COD removal rate was obtained at a current density of 93.3 A m⁻² and pH ranging from 4.5 to 6.5. At the optimum operational parameters for the experiments, electrocoagulation process could reduce COD from 1.1 g dm⁻³ to 78 mg dm⁻³, allowing direct discharge of the treated OMW as that meets the Algerian wastewater discharge standards (<125 mg dm⁻³).     

Investigation of municipal and olive mill wastewater co‐treatment in activated sludge–powdered activated carbon (AS‐PAC) systems

BACKGROUND: The purpose of this study was to investigate the co‐treatment of olive‐mill wastewater (OMW) and municipal wastewater in activated sludge systems operating in the absence and presence of different adsorbent materials and to study the role of sorption and biodegradation in total phenols removal. RESULTS: Batch experiments were initially conducted to investigate total phenols' adsorption capacity on activated sludge (AS), olive pomace (OP) and powdered activated carbon (PAC). According to the results, PAC presented the best adsorption capacity. Three sequencing batch reactors (SBRs) were also operated, treating municipal wastewater and different amounts of OMW. The first SBR contained AS (AS‐System), the second AS and OP (AS‐OP System) and the third AS and PAC (AS‐PAC System). All SBRs operated sufficiently in the presence of 1% v/v OMW, achieving mean COD and total phenols removal efficiency higher than 86% and 85%, respectively, and satisfactory settling capacity. Increase of OMW concentration to 5% v/v affected the performance of SBRs, resulting in mean COD removal efficiencies that ranged between 61% (AS‐OP System) and 80% (AS‐PAC System). CONCLUSION: Among the SBRs used, the AS‐PAC System operated with highest performance in the presence of 1 and 2.5% v/v OMW, and showed better stability in the presence of 5% v/v OMW. Calculation of total phenols mass flux revealed that biodegradation was the principal mechanism of their removal. The highest values of mean biotransformation rates were calculated for the AS‐PAC System and ranged between 2.0 and 40.6 d^?1 for different experimental phases. Copyright © 2012 Society of Chemical Industry     

Removal of organic load and phenolic compounds from olive mill wastewater by Fenton oxidation with zero-valent iron

Pre-treatment of olive mill wastewater (OMW) by Fenton Oxidation with zero-valent iron and hydrogen peroxide was investigated to improve phenolic compounds degradation and the chemical oxygen demand (COD) removal. Experimental procedure is performed with diluted OMW with COD 19 g/L and pH 5.2. The application of zero-valent Fe/H₂O₂ procedure allows high removal efficiency of pollutants from OMW. The optimal experimental conditions were found to be continuous presence of iron metal, acidic pH (2–4) and 1 M hydrogen peroxide solution. The experimental results show that the removal of 1 g of COD need 0.06 M of H₂O₂. At pH 1, the maximum COD removal (78%) is achieved after 1 h. Therefore, with a pH value within 2 and 4 the maximum COD removal reached 92%. Phenolic compounds are identified in treated and untreated OMW by gas chromatography coupled to mass spectrometry (GC–MS). The result shows a total degradation of phenolic compounds and an increasing biodegradability of treated OMW.     

The use of olive mill wastewater by wild type Yarrowia lipolytica strains: medium supplementation and surfactant presence effect

BACKGROUND: The aim of this work was to study the ability of two different wild type strains of the yeast Yarrowia lipolytica to grow on olive mill wastewater (OMW) and their potential to produce high‐value products such as lipases. Factors that affect cellular growth and OMW degradation were studied, such as nitrogen supplementation, cells concentration and surfactant addition. RESULTS: Both strains, W29 and IMUFRJ 50682, were able to grow in OMW with 19 g L^?1 of COD and approximately 800 mg L^?1 of total phenols concentration. The strain W29 presented the highest potential for extracellular lipase production in OMW medium. Lipase productivity was improved by the medium supplementation with ammonium sulphate up to 6 g L^?1, leading to 80% of COD degradation and 70% of total phenols reduction. The surfactant Tween 80 enhanced cell growth and COD degradation, but had a negative effect on lipase activity. CONCLUSIONS Y. lipolytica has a great potential for OMW valorisation by its use as culture medium for biomass and enzymes production. The operating conditions that favoured lipase production differ from the conditions that improve COD reduction. Copyright © 2008 Society of Chemical Industry     

Improvement of dye electrochemical treatment by combination with ultrasound technique

BACKGROUND: Currently, the combination of conventional physicochemical techniques appears to be an attractive option to apply to wastewater treatment. In this work, a hybrid technique, called sonoelectrochemistry as a result of the combination of electrochemical and ultrasound technology, was undertaken in order to increase the efficiency of textile wastewater remediation. RESULTS: Results have demonstrated the superiority of the sonoelectrochemical process over each treatment alone. Although in the sonoelectrochemical treatment, the decolourisation rate of di‐azo dyes was lower than mono‐azo or diphenylnaphthylmethane dyes, in all cases a first‐order kinetic behaviour was detected. In addition, the influence of inert electrolyte concentration (Na₂SO₄) was assayed. On the other hand, colour removal was considerably faster than the decrease in chemical oxygen demand (COD), which was attributed to the ease of chromophore destruction. Hence, for example for Lissamine Green B the efficiency of sonoelectrochemical decolourisation was 95% compared with 60% of COD removal after 1 h treatment. Additionally, a flow system with total reflux by the electrochemical and the sonoelectrochemical treatment was considered and a similar behaviour to previous experiments was found. CONCLUSIONS: Based on the results obtained, the feasibility of this hybrid technique was demonstrated. Furthermore, an efficient flow system was devised for dye decolourisation, which could be extrapolated to develop a continuous process. Copyright © 2009 Society of Chemical Industry     

A comparative study of azo dye decolorization by electro‐Fenton in two common electrolytes

BACKGROUND: This study compared the decolorization behaviors of a model azo dye of methyl red in Na₂SO₄ and NaCl media by electro‐Fenton process, in which FeSO₄ was added into the solution, while H₂O₂ was efficiently generated on a graphite–polytetrafluoroethylene cathode. Parameters such as pH, cathodic potential, electrolyte concentration, and initial dye concentration as well as the treatment time were investigated to disclose different decolorization behaviour. RESULTS: Decolorization in NaCl medium had an advantage over that in Na₂SO₄ medium not only in performance but also in its suitability for application, which seemed less sensitive to variations in parameters and thus broadened the optimal performance range. In NaCl medium, indirect oxidation by active chlorine contributed greatly to the decolorization, and the removal of methyl red obeyed pseudo‐first‐order kinetics. CONCLUSION: Electro‐Fenton oxidation in the present system in the presence of NaCl would is a promising procedure for azo dye waste‐water treatment. Copyright © 2009 Society of Chemical Industry     

Kinetic study of an anaerobic fluidized bed system used for the purification of fermented olive mill wastewater

The anaerobic digestion of olive mill wastewater (OMW) in a fluidized bed, pretreated with Geotrichum candidum, has been studied. The bioreactor used (volume = 3.5 dm³; biomass concentration = 11.5 g VSS dm^?3) maintained satisfactory operation for 4 to 35 days, in terms of hydraulic retention time, and removed 92% of the initial COD. The system was used to develop and test a kinetic model which was subsequently employed to determine growth yield and maintenance coefficient. From the results obtained, the Michaelis-Menten equation accurately described the substrate uptake (i.e. COD removal) in the anaerobic fluidized bed system. Pretreatment of the OMW was found to increase the rate of substrate uptake by a factor of 3.2 when compared to untreated OMW.     

Olive Mill and Winery Wastewaters Pre-Treatment by Coagulation with Chitosan

The pre-treatment of both winery wastewater (WW) and olive mill wastewater (OMW) by coagulation, using a natural organic coagulant, was investigated as a possible alternative to conventional metal based coagulants, in order to produce a potentially reusable organic sludge. Chitosan was chosen as a model natural organic coagulant and the coagulation process was optimized investigating different coagulant doses and pH values. In spite of the notably lower polluting load for the WW compared to the OMW, the efficiency of the chitosan coagulation was found to be high in terms of total suspended solids (81% and 80% for OMW and WW respectively) and turbidity (94% and 92% for OMW and WW respectively) removal for both wastewaters, but a notable difference was observed in terms of organic matter removal (32% and 73% in terms of COD for OMW and WW respectively). Taking into account that the best performances of the coagulation process by chitosan were achieved at the actual pH for OMW as well as no significant differences were observed for WW as the pH was changed, no chemicals addition is required to adjust pH.     

Treatment of Endocrine Disrupting Chemical From Aqueous Solution by Electrocoagulation

The removal of endocrine disrupting chemical (BPA; Bisphenol–A) from aqueous solution was experimentally investigated by electrocoagulation process. The effects of different combinations of aluminum (Al) and iron (Fe) electrode pair, supporting electrolyte type, supporting electrolyte concentration, initial pH and applied current density and initial BPA concentration on the Chemical Oxygen Demand (COD), and energy consumption performances were critically evaluated. The experiment results indicate that Al–Al electrode pair is the most efficient choice of the four electrode pairs. The COD removal efficiency was increased when NaCl was used as the supporting electrolyte instead of Na₂SO₄ and NaNO_3. The optimum supporting electrolyte type and its concentration, initial pH, applied current density and treatment time were found to be NaCl, 0.05 M, pH 7.0, 12 mA cm^?2 and 40 min, respectively. Energy consumption was found to decrease with increase of NaCl concentration while it increases with increasing applied current density. The initial and treated sample was characterized by UV–vis spectroscopy to confirm the treatment efficiency. The sludge formed during electrocoagulation was characterized by XRD and SEM/EDAX analysis.     

Electrochemical oxidation of Basic Blue 3 dye using a diamond anode: evaluation of colour,COD and toxicity removal

BACKGROUND: Textile industries generate considerable amounts of waste‐water, which may contain strong colour, suspended particles, salts, high pH and high chemical oxygen demand (COD) concentration. The disposal of these coloured wastewaters poses a major problem for the industry as well as a threat to the environment. In this study, electrochemical oxidation of Basic Blue 3 (BB3) dye was studied in a bipolar trickle tower (BTT) reactor using Raschig ring shaped boron‐doped diamond (BDD) electrodes in recirculated batch mode. The effects of current density, temperature, flow rate, sodium sulfate concentration (Na₂SO₄) as supporting electrolyte, and initial dye concentration were investigated. RESULTS: The best experimental conditions obtained were as follows: current density 0.875 mA cm^?2, temperature 30 °C, flow rate 109.5 mL min^?1, Na₂SO₄ concentration 0.01 mol L^?1. Under these conditions, 99% colour and 86.7% COD removal were achieved. Toxicity tests were also performed on BB3 solutions under the best experimental conditions. CONCLUSION: Based on these results, the BDD anode was found to be very successful for the simultaneous degradation of BB3 and removal of COD. Additional toxicity test results also showed that electrochemical treatment using a BDD Raschig ring anode in a BTT reactor is an effective way of reducing toxicity as well as removing colour and COD. Copyright © 2010 Society of Chemical Industry     

Effects of Cl-based chemical coagulants on electrochemical oxidation of textile wastewater

As a supporting electrolyte and the source of chloride reactant, NaCl is generally added for the electrochemical oxidation process. In this study, Cl-based chemical coagulation was employed as the pretreatment step for the preremoval of suspended and colloidal solids which impede electrochemical oxidation. It was adopted for the purpose of providing the source of the chloride reactant for the electrochemical oxidation. It was ultimately intended to omit the artificial addition of electrolyte solution and to decrease the pollutant loading efficiently on the post electrochemical oxidation process in order to improve the performance of organics removal. PAC and FeCl₃, Cl-based chemical coagulants, were successfully employed as the pretreatment step of electrochemical oxidation. PAC and FeCl₃, were able to achieve sufficient removal efficiency of organics as well as to exclude the artificial addition of a supporting electrolyte and the source of a chloride reactant.     

On the behaviour of doped SnO2 anodes stabilized with platinum in the electrochemical degradation of reactive dyes

In this paper the electrochemical characterisation of Ti/SnO₂-Sb-Pt anodes prepared by thermal decomposition is researched using different techniques. These results were also compared to those obtained for the Ti/SnO₂, Ti/SnO₂-Sb and deactivated Ti/SnO₂-Sb-Pt anodes. SECM technique confirmed the increase of electroactivity observed with the antimony doping and a little amount of platinum. In contrast, deactivated Ti/SnO₂-Sb-Pt anodes showed a drastic decrease in electroactivity. SEM and EDX analyses were also employed to evaluate the differences observed among these anodes. These results corroborated the high service life of Ti/SnO₂-Sb-Pt anodes being very useful for wastewater treatment. COD, HPLC, UV-vis and potential control measurements were also used to verify the viability of these anodes to degrade and decolourise wastewater solutions containing a reactive dye: C.I. Reactive Orange 4. With this purpose, different oxido-reduction electrolyses were carried out in presence of either 0.1 M Na₂SO₄ or 0.1 M NaCl as electrolyte. Although the use of NaCl gave the best results in decolourisation rate, the oxidation efficiency was practically the same independently of what type of electrolyte was used. It was also found that treated solutions presented oxidation-resistant intermediates as final products in all cases.     

Multi‐phase electro‐chemical catalytic oxidation of wastewater

The removal of organic pollutants from synthetic wash wastewater by a combined multi‐phase electro‐catalytic oxidation method was evaluated using porous graphite as anode and cathode, and CuO–Co₂O₃–PO₄^3? modified kaolin as catalyst. The synergic effect on COD removal was studied when integrating the electro‐chemical reactor with the effective modified kaolin in a single undivided cell; the results showed that higher COD removal efficiency was obtained than those obtained using the individual processes. Under optimal conditions of pH 3, 30 mA cm^?2 current density, very effective reduction of organic pollutants was achieved with this combined electro‐chemical method. High removal efficiency (90%) of the chemical oxygen demand (COD) was obtained in 60 min in the treatment of simulated wash wastewater (anionic surfactant, sodium dodecyl benzene sulfonate [DBS]). This method was also applied to treat wastewater form paper‐making and resulted in a COD reduction of 84%. Based on the investigation, a possible mechanism of this combined electro‐chemical process was proposed. The pollutants in wastewater could be decreased by the high reactive OH? that were produced via the decomposition of electro‐generated H₂O₂ activated by the synergic effect of electro‐field and catalyst. The results indicate that the multi‐phase catalytic electro‐chemical oxidation process is a promising technique for wastewater treatment. Copyright © 2006 Society of Chemical Industry     

Treatment of wastewaters from the olive mill industry by sonication

BACKGROUND: In this study, the effects of additives (manganese (III) oxide (Mn₃O₄), Cu⁺², Fe⁰ and potassium iodate (KIO₃)) and radical scavengers (sodium carbonate (Na₂CO₃), perfluorohexane (C₆F₁₄) and t‐buthyl alcohol (C₄H₁₀O)) on the dephenolization, decolorization, dearomatization and detoxification of olive mill wastewater (OMW) by sonication were investigated because wastewaters from this industry are not removed effectively. RESULTS: The maximum COD, color, total phenol and total aromatic amines (TAAs) removal efficiencies were 63, 82, 78 and 71%, respectively, at 60 °C with sonication only. The TAAs and phenol yields were increased to 96 and 97% with 6 mg L^?1 KIO₃ and 3 mg L^?1 Fe⁰ while color removal reached 97% with 6 mg L^?1 C₆F_14. The total annual cost with sonication only was 665 € m^?3 year^?1 while the cost slightly increased (666€ m³ year^?1) with C₆F₁₄. The maximum acute toxicity removals were 97‐98% in Daphnia magna and Vibrio fischeri The Microtox acute toxicity test was more sensitive than the Daphnia magna to the OMW samples. CONCLUSION: COD, color, total phenol, TAAs and toxicity in an OMW were removed efficiently and cost‐effectively by sonication. © 2012 Society of Chemical Industry     

Veratric acid treatment by anodic oxidation with BDD anode

BACKGROUND: Veratric acid (VA, 3,4‐dimethoxy‐benzoic acid) is representative of the polyphenolic type compounds present in olive mill wastewater (OMW). Given the bactericide factor, the inhibitor character and the anti bacteriological activity of this compound, traditional biological digestion cannot be applied and therefore new technologies, such as electrochemical oxidation using a boron‐doped diamond (BDD) anode have to be considered to avoid its accumulation in the environment. RESULTS: The electrochemical oxidation of aqueous solutions containing 1 mmol L^?1 VA has been investigated using a filter‐press reactor with a BDD anode during galvanostatic electrolysis. The influence of several operating parameters, such as applied current density, temperature, flow‐rate and supporting electrolyte concentration and type has been investigated. The experimental results showed that under the experimental conditions used the oxidation of VA was under mass‐transfer control and VA was completely degraded by the reaction with hydroxyl radicals electrogenerated at the BDD surface. The chemical oxygen demand (COD) decay kinetic followed a pseudo‐first‐order reaction and the apparent rate constant increased with flow rate and temperature. Under optimal experimental conditions of flow‐rate (300 L h^?1), temperature (35 °C) and current density (10 mA cm^?2), 99.5% of COD was removed during 2 h electrolysis, with 16.4 kWh m^?3 energy consumption. CONCLUSIONS: This study suggests that anodic oxidation with a BDD electrode is an excellent method for the treatment of effluents contaminated with VA and related polyphenols. Copyright © 2011 Society of Chemical Industry     

Isolation of a yeast,Trichosporon cutaneum,able to use low molecular weight phenolic compounds: application to olive mill waste water treatment

This study deals with the degradation of phenolic compounds in olive oil mill waste; a highly polluting material in olive oil‐producing countries because of its abundance and the toxicity of its phenolic compound content. This investigation confirms the ability of an isolated yeast, identified as Trichosporon cutaneum, to degrade phenolic compounds extracted from olive mill waste water (OMW). The yeast was adapted to the OMW by an enrichment culture. The results of this biotransformation were a decrease in the phenolic content and hence a reduction in the phytotoxic effects of the effluent after the yeast treatment. The kinetic growth of the isolated yeast on phenol over a range of concentrations (0.3–3.0 g dm^?3) was studied. The ability of the strain to assimilate simple monomeric phenols and alkyl phenols, at a concentration of 1 g dm^?3, in a synthetic liquid medium used as the sole carbon source was investigated in a batch culture. The aromatic ring cleavage pathway occurred in the yeast through catechol oxidation. Using various concentrations of ethyl acetate extract from OMW as the sole carbon source, the yeast exhibited growth on the substrate up to 7 g dm^?3 equivalent of phenols. A significant reduction of COD after the treatment of the OMW extract by the yeast isolate was noticed. The removal of phenol and COD exceeded 80% of the original loading after 8 days of treatment, for extracts containing initial COD in the range 19 to 72 g dm^?3. Copyright © 2004 Society of Chemical Industry     

Mineralization of the Pharmaceutical β-Blocker Atenolol by Means of Indirect Electrochemical Advanced Oxidation Process: Parametric and Kinetic Study

Atenolol is a β-blocker that can be found in urban wastewaters and which is not removed efficiently by conventional wastewater treatments. In the present study, electro-Fenton (EF) process was used to assess the degradation and mineralization of pharmaceutical atenolol in aqueous solutions. Electrolyses of 250 mL of atenolol solution (0.17 mM), at initial pH 3, were carried out in an undivided electrolytic cell in galvanostatic mode. Influence of material cathode (graphite, stainless steel, and platinized titanium), applied current (100–500 mA), sulfate dosage (0.01–0.5 M), and catalyst ferrous ions concentration (1–10 mM), on the oxidation efficiency was studied. Atenolol mineralization was monitored by COD dosage. Kinetic analysis indicated that atenolol mineralization followed a pseudo-first order model and the rate constant increased with rising current, ferrous ions concentration (up to 5 mM) and electrolyte concentration. Results showed that graphite cathode, 0.5 M Na₂SO₄ electrolyte, 0.3 A and 5 mM FeSO₄ catalyst were the best conditions for atenolol mineralization. In these optimal conditions, after 240 min more than 87% of the initial COD was removed. The corresponding current efficiency (CE) and specific energy consumption (SEC) were 22.33% and 0.194 kWh/kg COD, respectively. This latter corresponds to 0.078 kWh/m³ of treated wastewater.     

A compact process for the treatment of olive mill wastewater by combining OF and UV/H2O2 techniques

Olive oil production results in important quantities of wastewater containing large amounts of total solids and organic carbon as well as low oil concentrations. This paper describes the treatment of olive mill wastewater (OMW) by combining an ultrafiltration (UF) technique and an advanced oxidation process (AOP) using UV/H₂O₂. It further demonstrates the technical feasibility of this compact and stable process to remove a large part of total solids and organic carbon. Indeed, OF reduces the pollutants contained in the OMW with an apparent rejection coefficient R_COD in the range of 94%. The UV/H₂O₂ oxidation process may be easily used, in combination with UF, to finish the treatment of the permeate. The results obtained in batch and continuous mode showed that this technique offered a treated solution which complies with legal requirements. A final concentration of 17 mg_TOC dm⁻³ was obtained, which corresponds to a final COD of 52 mg dm⁻³, while the legal requirement is 125. Furthermore, the final effluent is fully decolorized.     

High level of laccases production by Trametes trogii culture on olive mill wastewater‐based media,application in textile dye decolorization

BACKGROUND: Laccases are receiving increasing attention as potential industrial enzymes in various applications. Therefore, it is important to find inexpensive and optimized media for large‐scale commercial production. The present work aims to valorize olive mill wastewater (OMW) by its use as base media for laccases production by Trametes trogii and use of the laccases produced for decolorizing textile dyes. RESULTS: A high yield of 25 120 U L^?1 of laccases was obtained at an OMW:water ratio of 80:20 enriched with 2 g L^?1 of urea corresponding to initial biochemical oxygen demand (BOD₅), chemical oxygen demand (COD) and total phenol concentrations of 18.4, 46 and 4.6 g L^?1 respectively. The partially purified laccases resulted in 85% decolorization of blue tubantin GLL 300 and black tubantin VSF 600, and 45% decolorization of blue solophenyl after 6 h of incubation. Subsequent additions of the same dye dose to the reaction mixture resulted in a very significant decrease in laccases activity after the third dye addition. CONCLUSION: The use of OMW for laccases production is a cost effective process. The laccases produced can be applied to the decolorization of textile wastewaters. Copyright © 2009 Society of Chemical Industry