Removal of Iodine-Containing X-ray Contrast Media from Environment: The Challenge of a Total Mineralization.

Iodinated X-ray contrast media (ICM) as emerging micropollutants have attracted considerable attention in recent years due to their high detected concentration in water systems. It results in environmental issues partly due to the formation of toxic by-products during the disinfection process in water treatment. Consequently, various approaches have been investigated by researchers in order to achieve ICM total mineralization. This review discusses the different methods that have been used to degrade them, with special attention to the mineralization yield and to the nature of formed by-products. The problem of pollution by ICM is discussed in the first part dedicated to the presence of ICM in the environment and its consequences. In the second part, the processes for ICM treatment including biological treatment, advanced oxidation/reductive processes, and coupled processes are reviewed in detail. The main results and mechanisms involved in each approach are described, and by-products identified during the different treatments are listed. Moreover, based on their efficiency and their cost-effectiveness, the prospects and process developments of ICM treatment are discussed.

Review: Clay-Modified Electrodes in Heterogeneous Electro-Fenton Process for Degradation of Organic Compounds: The Potential of Structural Fe(III) as Catalytic Sites.

Advanced oxidation processes are considered as a promising technology for the removal of persistent organic pollutants from industrial wastewaters. In particular, the heterogeneous electro-Fenton (HEF) process has several advantages such as allowing the working pH to be circumneutral or alkaline, recovering and reusing the catalyst and avoiding the release of iron in the environment as a secondary pollutant. Among different iron-containing catalysts, studies using clay-modified electrodes in HEF process are the focus in this review. Fe(III)/Fe(II) within the lattice of clay minerals can possibly serve as catalytic sites in HEF process. The description of the preparation and application of clay-modified electrodes in the degradation of model pollutants in HEF process is detailed in the review. The absence of mediators responsible for transferring electrons to structural Fe(III) and regenerating catalytic Fe(II) was considered as a milestone in the field. A comprehensive review of studies investigating the use of electron transfer mediators as well as the mechanism behind electron transfer from and to the clay mineral structure was assembled in order to uncover other milestones to be addressed in this study area.

A novel system coupling an electro-Fenton process and an advanced biological process to remove a pharmaceutical compound, metronidazole.

The objective of this study was to improve the mineralization of metronidazole, a recalcitrant antibiotic by the development of a new combined process coupling electro-Fenton and a biological process. For biotreatment, various strategies were considered bioaugmentation, bioacclimatation and biostimulation alone or combined. So, the novelty of this strategy is to combine advanced oxidation process with advanced biological process. The conventional biotreatment with activated sludge after 120 h of culture, led to 58.1% mineralization, whereas the pure isolated strains, from activated sludge culture in the presence of metronidazole by-products, identified as Pseudomonas putida (strain A) and Achromobacter sp. (strain B), led to 37.2% and 40.1% respectively. After original acclimation of the isolated strains to electrolysis by-products, the mineralization levels reached 75.6% and 72.9% for strains A and B respectively after 120 h of culture. The results showed that the mineralization of metronidazole by-products was the most important in the case of the combination of autochthonous bioaugmentation and biostimulation, with 96.1% after 120 h of treatment. By coupling the two processes, the global treatment reached therefore a mineralization yield of 97% with a reduction in processing time of 16 days compared to previous conventional biological treatment.

A New Approach to Produce Succinic Acid Through a Co-Culture System.

Microorganisms can produce a wide range of bio-based chemicals that can be used in various industrial applications as molecules of interest. In the present work, an analysis of the power production by pure culture, co-culture, and sequential culture was performed. In this study, both the mono-culture and the co-culture strategies of Actinobacillus succinogenes with Saccharomyces cerevisiae as carbon sources to produce succinic acid using glucose and fructose were examined. The cultures were performed in batch mode and a great attention was paid to the co-culture system to improve the biosynthetic pathway between A. succinogenes and S. cerevisiae by combining these two strains in a single fermentation process. Under microaerobic and anaerobic conditions, the process was characterized in terms of sugars concentration, cell density, metabolites, yield (mol-C products/ mol-C sugars), the temperature conditions for productivity, and pH. The results showed that the process could consume glucose and fructose and could adapt to different concentrations of the two sugars more quickly than by a single organism and the best results were obtained in a sequential co-culture recording 0.27 mol L-1 of succinic acid concentration and a volumetric productivity of 0.3 g L-1 h-1. Under the investigated operating conditions, the combination of these two strains in a single reactor produced a significant amount of succinic acid (0.70 mol-C SA/mol-C substrates). A simultaneous and sequential co-culture strategy can be a powerful new approach in the field of bio-based chemical production.

Electrochemical Processes Coupled to a Biological Treatment for the Removal of Iodinated X-ray Contrast Media Compounds.

Iodinated X-ray contrast media (ICM) compounds are a form of intravenous radiocontrast containing iodine, which are rapidly eliminated via urine or feces. The issue with the accumulation of ICM has received considerable critical attention since they are ubiquitously distributed in municipal wastewater effluents and in the aquatic environment and are not significantly eliminated by most biological sewage treatment processes. Among the methods that have been tested to eliminate ICM, electrochemical methods have significant advantages, since they can selectively cut the carbon-iodine bonds that are suspected to decrease their biodegradability. On the production sites, the recovery of iodine ions due to the carbon-iodine cleavage can be envisaged, which is particularly interesting to reduce the cost of the ICM production process. The coupling of an electrochemical process and a biological treatment can be carried out to mineralize the organic part of the formed by-products, allowing the recovery of the iodide ions. Therefore, the degradation of diatrizoate, a typical ionic ICM compound, by an electrochemical process was the purpose of this study. The electrochemical reduction of diatrizoate was performed using a flow cell with a graphite felt electrode at different potentials. The removal yield of diatrizoate reached ~100% in 2 h and the main product, 3,5-diacetamidobenzoic acid, was quantitatively formed, showing that diatrizoate was almost completely deiodinated. According to the BOD5/COD ratio, the biodegradability of diatrizoate after electrolysis was considerably improved. Cyclic voltammetry analysis of the electroreduced solution showed several oxidation peaks. The electrochemical oxidation of the by-products formed after the first treatment by electroreduction was then performed at three different potentials to study the influence of electrochemical oxidation on biodegradability. Results showed that the degradation yield of the deiodinated by-products increased with the potential and reached 100% at 1.3 V/SCE. Four different biological treatments were implemented during 21 days in stirred flasks with fresh activated sludge. The evolution of the mineralization during the biological treatment highlighted the biorecalcitrance of diatrizoate as previously estimated by the BOD5/COD ratio. Interestingly, the mineralization yield increased from 41 to 60% when electrochemical oxidation at 1.3 V/SCE was implemented after electroreduction.

Iron oxide nanoparticles as heterogeneous electro-Fenton catalysts for the removal of AR18 azo dye.

Heterogeneous electro-Fenton mineralization of Acid Red 18 (AR18) in aqueous solution was studied with magnetite Fe3O4 (MNPs) and haematite Fe2O3 (HNPs) nanoparticles as catalysts. High mineralization yields of AR18 were obtained with magnetite, 81% TOC removal after 180 min of electrolysis in 40 mg L-1 Fe3O4, pH 3.0, at 50 mA of current intensity and in 50 mM Na2SO4. In order to explain the obtained mineralization yield achieved with MNPs, the quantification of hydrogen peroxide (H2O2), hydroxyl radical (•OH) and iron leaching were performed at 50 and 100 mA. From the high iron concentration found in the bulk solution and the slight impact of the catalyst mass concentration on TOC removal, the formation of hydroxyl radicals occurs mainly through homogeneous process. In the presence of hydroxyl radical scavenger, degradation remained total after 15 min showing the involvement of a direct electrochemical oxidation of the dye at the electrode surface. The hydroxyl radical oxidation is responsible for at least 50% of mineralization.

Efficient Dechlorination of α-Halocarbonyl and α-Haloallyl Pollutants by Electroreduction on Bismuth.

The electrocatalytic activity of bismuth considered as a low-cost and green electrode material was studied in reductive dechlorination processes. Cyclic voltammetry analyses showed that the Bi electrode exhibited a high catalytic activity to reduce alachlor, a chlorinated herbicide, in the aqueous medium at different pH values. Bulk electrolyses were performed at different potentials and pH values. Alachlor was reduced in deschloroalachlor, its dechlorinated derivative, with a high selectivity (96%) and a current efficiency of 48%. The reductive dechlorination of other chlorinated compounds with an activated carbon atom was then studied, showing that the bismuth electrode catalyzed the electroreduction of chloroacetamides, α-halocarbonyl, and α-haloallyl pollutants. Cyclic voltammetry experiments allowed us to propose a mechanism explaining the high catalytic activity of bismuth to reduce these families of compounds.

Electro Fenton removal of clopyralid in soil washing effluents.

The removal of a commercial herbicide, based on clopyralid, by means of Electro-Fenton (EF) was studied using a soil washing effluent obtained using synthetic ground water as washing fluid. From the results, it was observed that the degradation and mineralization yields of clopyralid were high, even without the addition of supporting electrolyte. The groundwater could be then used as a sustainable supporting electrolyte. The influence of the minerals constituents, the current and the ferrous ions regeneration was evaluated. The highest hydrogen peroxide production was achieved working at 200 mA but regeneration of ferrous ions was not efficient at this current. Iodide ions were one of the main responsible in the EF efficiency decrease due to their reaction with the produced hydrogen peroxide. Electrochemical study proved that clopyralid was not electroactive and that its degradation was mainly due to radical oxidation. Long duration electrolysis carried out at 200 mA in groundwater provided an improvement of the solution biodegradability after 480 min that can be linked to a significant increase in the carboxylic acids production. These results support the feasibility of applying an EF process in order to carry out a subsequent biological mineralization.

Hybrid electrochemical and biological treatment of herbicidal ionic liquids comprising the MCPA anion.

The present study was focused on the application of an electrochemical oxidation process combined with biodegradation for the removal of novel Herbicidal Ionic Liquids (HILs) -promising protection plant products which incorporate herbicidal anions and ammonium cations. The influence of carbon chain length (n = 8, 10, 12, 14, 16, 18) in the dialkyldimethylammonium cations on electrochemical oxidation kinetics, degradation efficiency and biodegradation by activated sludge was investigated. It was established that the applied cation influenced the heterogeneous rate constant and diffusion coefficient of electrochemical oxidation. The oxidation efficiency ranged from 17% in case of HILs with C8 alkyl chain to approx. 60% in case of HILs comprising C14 and C16 alkyl chains after 3 h of electrochemical treatment. Subsequent biodegradation studies revealed that electrochemical oxidation improved the mineralization efficiency of the studied HILs. The mineralization efficiency of electrochemically-treated HILs ranged from 28% in case of HILs comprising the C8 alkyl chain to 57% in case of HILs with C14 and C16 alkyl chains after 28 days. In case of untreated HILs, the corresponding mineralization efficiency ranged from 0 to 8%, respectively. This confirms the feasibility of a hybrid electrochemical-biological approach for treatment of herbicidal ionic liquids based on MCPA.

Metronidazole removal by means of a combined system coupling an electro-Fenton process and a conventional biological treatment: By-products monitoring and performance enhancement.

In order to mineralize Metronidazole (MTZ), a process coupling an electro-Fenton pretreatment and a biological degradation was implemented. A mono-compartment batch reactor containing a carbon-felt cathode and a platinum anode was employed to carry out the electro-Fenton pretreatment of MTZ. A total degradation of MTZ (100 mg L-1) was observed at 0.07 mA.cm-2 after only 20 min of electrolysis. Yet, after 1 and 2 h of electrolysis, the mineralization level remained low (16.2% and 32% respectively), guaranteeing a significant residual organic content for further biological treatment. LCMS/MS was used to determine the intermediates by-products and hence to propose a plausible degradation pathway. An increase from 0 to 0.44 and 0.6 for 1 and 2 h of electrolysis was observed for the BOD5/COD ratio. Thus, from 1 h of electro-Fenton pretreatment, the electrolysis by-products were considered biodegradable. A biological treatment of the electrolysis by-products after 1 and 2 h was then realized. The mineralization yields reached very close values, about 84% for 1 and 2 h of electrolysis after 504 h of biological treatment, namely close to 89% for the overall process, showing the pertinence of the proposed coupled process.

Reactive oxygen and iron species monitoring to investigate the electro-Fenton performances. Impact of the electrochemical process on the biodegradability of metronidazole and its by-products.

In this study, the monitoring of reactive oxygen species and the regeneration of the ferrous ions catalyst were performed during electro-Fenton (EF) process to highlight the influence of operating parameters. The removal of metronidazole (MTZ) was implemented in an electrochemical mono-compartment batch reactor under various ranges of current densities, initial MTZ and ferrous ions concentrations, and pH values. It was found that under 0.07 mA cm-2, 0.1 mM of ferrous ions and pH = 3, the efficiency of 100 mg L-1 MTZ degradation and mineralization were 100% within 20 min and 40% within 135 min of electrolysis, respectively. The highest hydrogen peroxide and hydroxyl radical concentrations, 1.4 mM and 2.28 mM respectively, were obtained at 60 min electrolysis at 0.07 mA cm-2. Improvement of the biodegradability was reached from 60 min of electrolysis with a BOD5/COD ratio above 0.4, which was reinforced by a respirometric study, that supports the feasibility of coupling electro-Fenton and biological treatment for the metronidazole removal.

Combination of the Electro/Fe3+/peroxydisulfate (PDS) process with activated sludge culture for the degradation of sulfamethazine.

In this paper, the major factors affecting the degradation and the mineralization of sulfamethazine by Electro/Fe3+/peroxydisulfate (PDS) process (e.g. current density, PDS concentration, Fe3+ ions concentration and initial sulfamethazine (SMT) concentration) were evaluated. The relevance of this process as a pretreatment prior to activated sludge culture was also examined. Regarding the impact on SMT degradation and mineralization, the obtained results showed that they were significantly enhanced by increasing the current density and the PDS concentrations in the ranges 1-40mAcm-2 and from 1 to 10mM respectively; while they were negatively impacted by an increase of the initial SMT concentration and the Fe3+ concentration, from 0.18 to 0.36mM and from 1 to 4mM respectively. The optimal operating conditions were therefore 40mAcm-2 current density, 10mM PDS concentrations, 1mM Fe3+, and 0.18mM SMT. Indeed, under these conditions the degradation of SMT and its mineralization yield were 100% and 83% within 20min and 180min respectively. To ensure a significant residual organic content for activated sludge culture after Electro/Fe3+/PDS pre-treatment, the biodegradability test and the biological treatment were performed on a solution electrolyzed at 40mAcm-2, 10mM PDS concentrations, 1mM Fe3+, and 0.36mM SMT. Under these conditions the BOD5/COD ratio increased from 0.07 to 0.41 within 6h of electrolysis time. The subsequent biological treatment increased the mineralization yield to 86% after 30days, confirming the relevance of the proposed combined process.

Direct and indirect electrochemical reduction prior to a biological treatment for dimetridazole removal.

Two different electrochemical reduction processes for the removal of dimetridazole, a nitroimidazole-based antibiotic, were examined in this work. A direct electrochemical reduction was first carried out in a home-made flow cell in acidic medium at potentials chosen to minimize the formation of amino derivatives and then the formation of azo dimer. Analysis of the electrolyzed solution showed a total degradation of dimetridazole and the BOD5/COD ratio increased from 0.13 to 0.24. An indirect electrochemical reduction in the presence of titanocene dichloride ((C5H5)2TiCl2), which is used to reduce selectively nitro compounds, was then investigated to favour the formation of amino compounds over hydroxylamines and then to prevent the formation of azo and azoxy dimers. UPLC-MS/MS analyses showed a higher selectivity towards the formation of the amino compound for indirect electrolyses performed at pH 2. To confirm the effectiveness of the electrochemical reduction, a biological treatment involving activated sludge was then carried out after direct and indirect electrolyses at different pH. The enhancement of the biodegradability was clearly shown since mineralization yields of all electrolyzed solutions increased significantly.

Removal of herbicidal ionic liquids by electrochemical advanced oxidation processes combined with biological treatment.

Recently a new group of ionic liquids (ILs) with herbicidal properties has been proposed for use in agriculture. Owing to the design of specific physicochemical properties, this group, referred to as herbicidal ionic liquids (HILs), allows for reducing herbicide field doses. Several ILs comprising phenoxy herbicides as anions and quaternary ammonium cations have been synthesized and tested under greenhouse and field conditions. However, since they are to be introduced into the environment, appropriate treatment technologies should be developed in order to ensure their proper removal and avoid possible contamination. In this study, didecyldimethylammonium (4-chloro-2-methylphenoxy) acetate was selected as a model HIL to evaluate the efficiency of a hybrid treatment method. Electrochemical oxidation or electro-Fenton was considered as a pretreatment step, whereas biodegradation was selected as the secondary treatment method. Both processes were carried out in current mode, at 10 mA with carbon felt as working electrode. The efficiency of degradation, oxidation and mineralization was evaluated after 6 h. Both processes decreased the total organic carbon and chemical oxygen demand (COD) values and increased the biochemical oxygen demand (BOD5) on the COD ratio to a value close to 0.4, showing that the electrolyzed solutions can be considered as 'readily biodegradable.'

Sulfamethazine removal by means of a combined process coupling an oxidation pretreatment and activated sludge culture - preliminary results.

A coupled electrochemical process and biological treatment was used to remove a biorecalcitrant antibiotic: sulfamethazine (SMT). The pretreatment was performed in a home-made flow cell involving graphite felt as a working electrode at potentials of 1 and 1.6 V/saturated calomel electrode (SCE); it was followed by a biological process involving activated sludge purchased from a local wastewater treatment plant. Activated sludge cultures of pretreated and non-pretreated SMT solution were carried out for 3 weeks, and different parameters were monitored, especially total organic carbon (TOC) and SMT concentrations. high-performance liquid chromatography results revealed that the target molecule was not assimilated by activated sludge. However, and confirming the improvement previously observed for the biological oxygen demand/chemical oxygen demand (BOD5/COD) ratio, from 0.08 before electrolysis to 0.58 after electrolysis, a pretreatment step in oxidation at 1.6 V/SCE led to a fast decrease of TOC during the subsequent biological treatment, since the mineralization yields increased from 10% for a non-pretreated SMT solution to 76.6% after electrolysis in oxidation (1.6 V/SCE), confirming the efficiency of coupling the electro-oxidation process with a biological treatment for the mineralization of SMT. Moreover, when the electrolysis was performed at 1 V/SCE, no biodegradation was observed, underlining the importance of the electrochemical pretreatment.

Degradation of enoxacin antibiotic by the electro-Fenton process: Optimization, biodegradability improvement and degradation mechanism.

This study aims to investigate the effectiveness of the electro-Fenton process on the removal of a second generation of fluoroquinolone, enoxacin. The electrochemical reactor involved a carbon-felt cathode and a platinum anode. The influence of some experimental parameters, namely the initial enoxacin concentration, the applied current intensity and the Fe(II) amount, was examined. The degradation of the target molecule was accompanied by an increase of the biodegradability, assessed from the BOD5 on COD ratio, which increased from 0 before treatment until 0.5 after 180 min of electrolysis at 50 mg L(-1) initial enoxacin concentration, 0.2 mmol L(-1) Fe(II) concentration and 300 mA applied current intensity. TOC and COD time-courses were also evaluated during electrolysis and reached maximum residual yields of 54% and 43% after 120 min of treatment, respectively. Moreover, a simultaneous generation of inorganic ions (fluorides, ammonium and nitrates) were observed and 3 short chain carboxylic acids (formic, acetic and oxalic acids) were identified and monitored during 180 min of electrolysis. By-products were identified according to UPLC-MS/MS results and a degradation pathway was proposed.

Removal of a mixture tetracycline-tylosin from water based on anodic oxidation on a glassy carbon electrode coupled to activated sludge.

The purpose of this study was first to examine the electrochemical oxidation of two antibiotics, tetracycline (TC) and tylosin (Tylo), considered separately or in mixture, on a glassy carbon electrode in aqueous solutions; and then to assess the relevance of such electrochemical process as a pre-treatment prior to a biological treatment (activated sludge) for the removal of these antibiotics. The influence of the working potential and the initial concentration of TC and Tylo on the electrochemical pre-treatment process was also investigated. It was noticed that antibiotics degradation was favoured at high potential (2.4 V/ saturated calomel electrode (SCE)), achieving total degradation after 50 min for TC and 40 min for Tylo for 50 mg L(-1) initial concentration, with a higher mineralization efficiency in the case of TC. The biological oxygen demand in 5 days (BOD5)/Chemical oxygen demand (COD) ratio increased substantially, from 0.033 to 0.39 and from 0.038 to 0.50 for TC and Tylo, respectively. Regarding the mixture (TC and Tylo), the mineralization yield increased from 10.6% to 30.0% within 60 min of reaction time when the potential increased from 1.5 to 2.4 V/SCE and the BOD5/COD ratio increased substantially from 0.010 initially to 0.29 after 6 h of electrochemical pre-treatment. A biological treatment was, therefore, performed aerobically during 30 days, leading to an overall decrease of 72% of the dissolved organic carbon by means of the combined process.

Photocatalytic degradation of bezacryl yellow in batch reactors--feasibility of the combination of photocatalysis and a biological treatment.

A combined process coupling photocatalysis and a biological treatment was investigated for the removal of Bezacryl yellow (BZY), an industrial-use textile dye. Photocatalytic degradation experiments of BZY were carried out in two stirred reactors, operating in batch mode with internal or external irradiation. Two photocatalysts (TiO2P25 and TiO2PC500) were tested and the dye degradation was studied for different initial pollutant concentrations (10-117 mg L(-1)). A comparative study showed that the photocatalytic degradation led to the highest degradation and mineralization yields in a stirred reactor with internal irradiation in the presence of the P25 catalyst. Regardless of the photocatalyst, discoloration yields up to 99% were obtained for 10 and 20 mg L(-1) dye concentrations in the reactor with internal irradiation. Moreover, the first-order kinetic and Langmuir-Hinshelwood models were examined by using the nonlinear method for different initial concentrations and showed that the two models lead to completely different predicted kinetics suggesting that they were completely different.According to the BOD5/ Chemical oxygen demand (COD) ratio, the non-treated solution (20 mg L(-1) of BZY) was estimated as non-biodegradable. After photocatalytic pretreatment of bezacryl solution containing 20 mg/L of initial dye, the biodegradability test showed a BOD5/COD ratio of 0.5, which is above the limit of biodegradability (0.4). These results were promising regarding the feasibility of combining photocatalysis and biological mineralization for the removal of BZY.

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.

Integration of photocatalysis and biological treatment for azo dye removal--application to AR183.

The feasibility of coupling photocatalysis with biological treatment to treat effluents containing azo dyes was examined in this work. With this aim, the degradation of Acid Red 183 was investigated. The very low biodegradability of AR183 was confirmed beforehand by measuring the biological oxygen demand (BOD5). Photocatalysis experiments were carried out in a closed-loop step photoreactor. The reactor walls were covered by TiO2 catalyst coated on non-woven paper, and the effluent flowed over the photocatalyst as a thin falling film. The removal of the dye was 82.7% after 4 h, and a quasi-complete decolorization (98.5%) was obtained for 10 h of irradiation (initial concentration 100 mg L(-1)). The decrease in concentration followed pseudo-first-order kinetics, with a constant k of 0.47 h(-1). Mineralization and oxidation yields were 80% and 75%, respectively, after 10 h of pretreatment. Therefore, even if target compound oxidation occurs (COD removal), indicating a modification to the chemical structure, the concomitant high mineralization was not in favour of subsequent microbial growth. The BOD5 measurement confirmed the non-biodegradability of the irradiated solution, which remained toxic since the EC50 decreased from 35 to 3 mg L(-1). The proposed integrated process appeared, therefore, to be not relevant for the treatment of AR183. However, this result should be confirmed for other azo dyes.