Search

The main objective of this study was to generate ready-to-use revalorized irrigation water for fertilization from urban wastewater treatment plant (UWWTP) effluents. The focus was on controlled retention of NH 4 + and microcontaminants (MC), using nanofiltration. Retentates generated were treated by solar photo-Fenton at circumneutral pH using Ethylenediamine-N, N'-disuccinic acid (EDDS) iron complexing agent. Solar photo-Fenton degradation efficacy was compared with electrooxidation processes as anodic oxidation, solar-assisted anodic oxidation, electro-Fenton and solar photoelectro Fenton. Finally, phytotoxicity and acute toxicity tests were performed to demonstrate the potentially safe reuse of treated wastewater for crop irrigation. Nanofiltration was able to produce a ready-to-use permeate stream containing recovered NH 4 + . (valuable nutrient). Solar photo-Fenton treatment at circumneutral pH would only be of interest for rapid degradation of contaminants at less than 1 mg/L in nanofiltration retentates. Other alternative tertiary treatments, such as electrooxidation processes, are a promising alternative when a high concentration of MC requires longer process times. Anodic oxidation was demonstrated to be able to eliminate >80% of microcontaminants and solar-assisted anodic oxidation significantly reduced the electricity consumption. Electro-Fenton processes were the least efficient of the processes tested. Phytotoxicity results showed that irrigation with the permeates reduced germination, root development was mainly promoted and shoot development was positive only at low retention rate (concentration factor = 2). Acute and chronic Daphnia magna toxicity studies demonstrated that the permeate volumes should be diluted at least 50% before direct reuse for crop irrigation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The application of electrochemical processes for wastewater treatment has increase significantly in the last two decades. However, most of the works are focused on lab-scale systems testing in saline simulated solutions spiked with a reference organic compound, evidencing the scarcity of studies on actual wastewaters through a more realistic practical approach. The aim of the present work is assessing the performance of electrochemical treatments in actual matrices, considering the formation of different oxidants species, apart from hydroxyl radicals, from dissolved ions contained in target effluents as well as both, the regeneration of Fe 2+ and their combination with a light irradiation source. The degradation of a mix of microcontaminants in water matrices with different complexity by solar photoelectron-Fenton at natural pH and at pilot scale has been carried out at Plataforma Solar de Almería. Higher degradation rates were obtained when focusing on the more complex and saline matrices. In addition, complex industrial wastewaters mineralization was also studied by means of solar assisted electro-oxidation, showing the crucial role of ammonium concentration in the effluent, since it acts as a competitor for active chlorine species and so reducing the mineralization rate., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The effect of the UV-C/free chlorine (FC) process on the removal of contaminants of emerging concern (CECs) from real urban wastewater as well as the effect of UV-C radiation on the formation of trihalomethanes (THMs) compared to FC process alone was investigated. Unlike of FC process, UV-C/FC was really effective in the degradation of the target CECs (carbamazepine (CBZ), diclofenac, sulfamethoxazole and imidacloprid) in real wastewater (87% degradation of total CECs within 60 min, Q UVC  = 1.33 kJ L -1 ), being CBZ the most refractory one (49.5%, after 60 min). The UV-C radiation significantly affected the formation of THMs. THMs concentration (mainly chloroform) was lower in UV-C/FC process after 30 min treatment (<1 μgL -1  = limit of quantification (LOQ)) than in FC process in dark (2.3 μgL -1 ). Noteworthy, while in FC treated wastewater chloroform concentration increased after treatment, UV-C/FC process resulted in a significant decrease (residual concentrations below the LOQ), even after 24 h and 48 h post-treatment incubation. The formation of radicals due to UV-C/FC process can reduce THMs compared to chlorination process, because part of FC reacts with UV-C radiation to form radicals and it is no longer available to form THMs. These results are encouraging in terms of possible use of UV-C/FC process as advanced treatment of urban wastewater even for possible effluent reuse., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The removal of contaminants of emerging concern (CECs) from urban wastewater treatment plants (UWTPs) is really important to minimize the risk for human health and environment. In this study, the homogeneous advanced oxidation process (AOP) UV-C/free chlorine (UV-C/FC) was investigated at pilot scale in the degradation of a mixture of four CECs, in different water matrices and compared to a consolidated AOP, namely UV-C/H 2 O 2 . As matter of fact 90% degradation of CECs was observed after 15 min (Q UVC  = 0.33 kJ L -1 ) by UV-C/FC (5 mg L -1 of FC) and 30 min (0.67 kJ L -1 ) by UV-C/H 2 O 2 (5 mg L -1 of H 2 O 2 ) in natural water. However, CECs degradation by UV-C/H 2 O 2 and UV-C/FC was comparable (>82%) in wastewater samples, under the investigated conditions (60 min, 1.33 kJ L -1 ). The effect of sunlight/FC process on the target CECs was also investigated (in a compound parabolic collector based reactor). Interestingly, a different behaviour was observed between the two light sources. In particular, a total removal of carbamazepine (CBZ) and imidacloprid (IMD) was observed for UV-C/FC process with 0.27 kJ L -1 and 10 mgL -1 of FC, while, in the sunlight/FC process (same FC dose), CBZ total removal took place quite fast (0.50 kJ L -1 ), but 90% removal of IMD was observed only after 60 min (7.09 kJ L -1 ). In conclusion, UV-C/FC process can be an interesting solution for tertiary treatment of urban wastewater for the removal of CECs and sunlight/FC is worthy of further investigation to evaluate its possible application in small UWTPs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The aim of this work was to investigate the treatment of the artificial sweetener saccharin (SAC) in a solar compound parabolic collector pilot plant by means of the photo-Fenton process at pH 2.8. Olive mill wastewater (OMW) was used as iron chelating agent to avoid acidification of water at pH 2.8. For comparative purposes, Ethylenediamine-N, N-disuccinic acid (EDDS), a well-studied iron chelator, was also employed at circumneutral pH. Degradation products formed along treatment were identified by LC-QTOF-MS analysis. Their degradation was associated with toxicity removal, evaluated by monitoring changes in the bioluminescence of Vibrio fischeri bacteria. Results showed that conventional photo-Fenton at pH 2.8 could easily degrade SAC and its intermediates yielding k, apparent reaction rate constant, in the range of 0.64-0.82 L kJ -1 , as well as, eliminate effluent's chronic toxicity. Both OMW and EDDS formed iron-complexes able to catalyse H 2 O 2 decomposition and generate HO. OMW yielded lower SAC oxidation rates (k = 0.05-0.1 L kJ -1 ) than EDDS (k = 2.21-7.88 L kJ -1 ) possibly due to its higher TOC contribution. However, the degradation rates were improved (k = 0.13 L kJ -1 ) by increasing OMW dilution in the reactant mixture. All in all, encouraging results were obtained by using OMW as iron chelating agent, thus rendering this approach promising towards the increase of process sustainability., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Industrial preparation of cork consists of its immersion for approximately 1 hour in boiling water. The use of herbicides and pesticides in oak tree forests leads to absorption of these compounds by cork; thus, after boiling process, they are present in wastewater. Cork boiling wastewater shows low biodegradability and high acute toxicity involving partial inhibition of their biodegradation when conventional biological treatment is applied. In this work, a treatment line strategy based on the combination of advanced physicochemical technologies is proposed. The final objective is the reuse of wastewater in the cork boiling process; thus, reducing consumption of fresh water in the industrial process itself. Coagulation pre-treatment with 0.5 g/L of FeCl 3 attained the highest turbidity elimination (86 %) and 29 % of DOC elimination. Similar DOC removal was attained when using 1 g/L of ECOTAN BIO (selected for ozonation tests), accompanied of 64 % of turbidity removal. Ozonation treatments showed less efficiency in the complete oxidation of cork boiling wastewater, compared to solar photo-Fenton process, under the studied conditions. Nanofiltration system was successfully employed as a final purification step with the aim of obtaining a high-quality reusable permeate stream. Monitoring of unknown compounds by LC-QTOF-MS allowed the qualitative evaluation of the whole process. Acute and chronic toxicity as well as biodegradability assays were performed throughout the whole proposed treatment line.

This work reports the treatment of a mature landfill leachate through the application of chemical-based treatment processes in order to achieve the discharge legal limits into natural water courses. Firstly, the effect of coagulation/flocculation with different chemicals was studied, evaluating the role of different initial pH and chemicals concentration. Afterwards, the efficiency of two different advanced oxidation processes for leachate remediation was assessed. Fenton and solar photo-Fenton processes were applied alone and in combination with a coagulation/flocculation pre-treatment. This physicochemical conditioning step, with 2 g L(-1) of FeCl3 · 6H2O at pH 5, allowed removing 63% of COD, 80% of turbidity and 74% of total polyphenols. Combining the coagulation/flocculation pre-treatment with Fenton reagent, it was possible to reach 89% of COD removal in 96 h. Moreover, coagulation/flocculation combined with solar photo-Fenton revealed higher DOC (75%) reductions than single solar photo-Fenton (54%). In the combined treatment (coagulation/flocculation and solar photo-Fenton), it was reached a DOC reduction of 50% after the chemical oxidation, with 110 kJ L(-1) of accumulated UV energy and a H2O2 consumption of 116 mM. Toxicity and biodegradability assays were performed to evaluate possible variations along the oxidation processes. After the combined treatment, the leachate under study presented non-toxicity but biodegradability increased., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In view of the inefficient elimination of micro-pollutants by today's conventional biological treatments and new legislation requiring elimination of at least 80 % of their concentration, the application of an advanced tertiary treatment must be studied. A good option would be advanced oxidation processes (AOPs), which have very often been combined with physicochemical pre-treatSments to increase efficiency or reduce operating costs. This study focused on the combination of membrane nanofiltration and solar photo-Fenton for the main purpose of removing five pharmaceuticals (sulfamethoxazole, ibuprofen, ofloxacin, carbamazepine and flumequine) from real MWTP effluents under realistic conditions (μg L(-1)). This research also included tests performed with modified photo-Fenton using a low iron concentration at circumneutral pH and a low hydrogen peroxide dose, in an attempt to reduce major treatment costs. Over 80 % of dissolved organic carbon, chemical oxygen demand and turbidity were also retained during nanofiltration, making pharmaceutical removal less efficient in terms of concentrate treatment time than direct treatment, i.e. the concentrate illumination time was around 150 min while direct treatment was around 40 min. Nevertheless, it should be highlighted that, although no savings in installation costs was observed for the combined system (nanofiltration/solar photo-Fenton), the reaction rate improved and so, there was a savings in reagent costs (mainly hydrogen peroxide and sulfuric acid).

Today, environmental impact associated with pollution treatment is a matter of great concern. A method is proposed for evaluating environmental risk associated with Advanced Oxidation Processes (AOPs) applied to wastewater treatment. The method is based on the type of pollution (wastewater, solids, air or soil) and on materials and energy consumption. An Environmental Risk Index (E), constructed from numerical criteria provided, is presented for environmental comparison of processes and/or operations. The Operation Environmental Risk Index (EOi) for each of the unit operations involved in the process and the Aspects Environmental Risk Index (EAj) for process conditions were also estimated. Relative indexes were calculated to evaluate the risk of each operation (E/NOP) or aspect (E/NAS) involved in the process, and the percentage of the maximum achievable for each operation and aspect was found. A practical application of the method is presented for two AOPs: photo-Fenton and heterogeneous photocatalysis with suspended TiO2 in Solarbox. The results report the environmental risks associated with each process, so that AOPs tested and the operations involved with them can be compared.

In recent years, membrane technologies (nanofiltration (NF)/reverse osmosis (RO)) have received much attention for micropollutant separation from Municipal Wastewater Treatment Plant (MWTP) effluents. Practically all micropollutants are retained in the concentrate stream, which must be treated. Advanced Oxidation Processes (AOPs) have been demonstrated to be a good option for the removal of microcontaminants from water systems. However, these processes are expensive, and therefore, are usually combined with other techniques (such as membrane systems) in an attempt at cost reduction. One of the main costs in solar photo-Fenton comes from reagent consumption, mainly hydrogen peroxide and chemicals for pH adjustment. Thus, in this study, solar photo-Fenton was used to treat a real MWTP effluent with low initial iron (less than 0.2 mM) and hydrogen peroxide (less than 2 mM) concentrations. In order to work at neutral pH, iron complexing agents (EDDS and citrate) were used in the two cases studied: direct treatment of the MWTP effluent and treatment of the concentrate stream generated by NF. The degradation of five pharmaceuticals (carbamazepine, flumequine, ibuprofen, ofloxacin and sulfamethoxazole) spiked in the effluent at low initial concentrations (μg L(-1)) was monitored as the main variable in the pilot-plant-scale photo-Fenton experiments. In both effluents, pharmaceuticals were efficiently removed (>90%), requiring low accumulated solar energy (2 kJUV L(-1), key parameter in scaling up the CPC photoreactor) and low iron and hydrogen peroxide concentrations (reagent costs, 0.1 and 1.5 mM, respectively). NF provided a clean effluent, and the concentrate was positively treated by solar photo-Fenton with no significant differences between the direct MWTP effluent and NF concentrate treatments., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The presence of pathogenic antibiotic-resistant bacteria in aquatic environments has become a health threat in the last few years. Their presence has increased due to the presence of antibiotics in wastewater effluents, which are not efficiently removed by conventional wastewater treatments. As a result there is a need to study the possible ways of removal of the mixtures of antibiotics present in wastewater effluents and the antibiotic-resistant bacteria, which may also spread the antibiotic resistance genes to other bacterial populations. In this study the degradation of a mixture of antibiotics i.e. sulfamethoxazole and clarithromycin, the disinfection of total enterococci and the removal of those resistant to: a) sulfamethoxazole, b) clarithromycin and c) to both antibiotics have been examined, along with the toxicity of the whole effluent mixture after treatment to the luminescent aquatic bacterium Vibrio fischeri. Solar Fenton treatment (natural solar driven oxidation) using Fenton reagent doses of 50 mg L(-1) of hydrogen peroxide and 5 mg L(-1) of Fe(3+) in a pilot-scale compound parabolic collector plant was used to examine the disinfection and antibiotic resistance removal efficiency in different aqueous matrices, namely distilled water, simulated and real wastewater effluents. There was a faster complete removal of enterococci and of antibiotics in all aqueous matrices by applying solar Fenton when compared to photolytic treatment of the matrices. Sulfamethoxazole was more efficiently degraded than clarithromycin in all three aqueous matrices (95% removal of sulfamethoxazole and 70% removal of clarithromycin in real wastewater). The antibiotic resistance of enterococci towards both antibiotics exhibited a 5-log reduction with solar Fenton in real wastewater effluent. Also after solar Fenton treatment, there were 10 times more antibiotic-resistant enterococci in the presence of sulfamethoxazole than in the presence of clarithromycin. Finally, the toxicity of the treated wastewater to V. fischeri remained very low throughout the treatment time., (© 2013.)

This study compares two different solar photo-Fenton processes, conventional photo-Fenton at pH3 and modified photo-Fenton at neutral pH with minimal Fe (5 mg L⁻¹) and minimal initial H₂O₂ (50 mg L⁻¹) concentrations for the degradation of emerging contaminants in Municipal Wastewater Treatment Plants effluents in solar pilot plant. As Fe precipitates at neutral pH, complexing agents which are able to form photoactive species, do not pollute the environment or increase toxicity have to be used to keep the iron in solution. This study was done using real effluents containing over 60 different contaminants, which were monitored during treatment by liquid chromatography coupled to a hybrid quadrupole/linear ion trap mass analyzer (LC-QTRAP-MS/MS) operating in selected reaction monitoring (SRM) mode. Concentrations of the selected contaminants ranged from a few ng L⁻¹ to tens of μg L⁻¹. It was demonstrated in all cases the removal of over 95% of the contaminants. Photo-Fenton at pH3 provided the best treatment time, but has the disadvantage that the water must be previously acidified. The most promising process was photo-Fenton modified with Ethylenediamine-N,N'-disuccinic acid (EDDS), as the pH remained in the neutral range., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The photo-Fenton degradation of paracetamol (PCT) was evaluated using FeSO(4) and the iron complex potassium ferrioxalate (FeOx) as iron source under simulated solar light. The efficiency of the degradation process was evaluated considering the decay of PCT and total organic carbon concentration and the generation of carboxylic acids, ammonium and nitrate, expressed as total nitrogen. The results showed that the degradation was favored in the presence of FeSO(4) in relation to FeOx. The higher concentration of hydroxylated intermediates generated in the presence of FeSO(4) in relation to FeOx probably enhanced the reduction of Fe(III) to Fe(II) improving the degradation efficiency. The degradation products were determined using liquid chromatography electrospray time-of-flight mass spectrometry. Although at different concentrations, the same intermediates were generated using either FeSO(4) or FeOx, which were mainly products of hydroxylation reactions and acetamide. The toxicity of the sample for Vibrio fischeri and Daphnia magna decreased from 100% to less than 40% during photo-Fenton treatment in the presence of both iron species, except for D. magna in the presence of FeOx due to the toxicity of oxalate to this organism. The considerable decrease of the sample toxicity during photo-Fenton treatment using FeSO(4) indicates a safe application of the process for the removal of this pharmaceutical., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The pilot-scale solar degradation of trimethoprim (TMP) in different water matrices (demineralized water: DW, simulated natural freshwater: SW; simulated wastewater: SWW; and real effluent: RE) was investigated in this study. DOC removal was lower in the case of SW compared to DW, which can be attributed to the presence of inorganic anions which may act as scavengers of the HO·. Furthermore, the presence of organic carbon and higher salt content in SWW and RE led to lower mineralization per dose of hydrogen peroxide compared to DW and SW. Toxicity assays in SWW and RE were also performed indicating that toxicity is attributed to the compounds present in RE and their by-products formed during solar Fenton treatment and not to the intermediates formed by the oxidation of TMP. A large number of compounds generated by the photocatalytic transformation of TMP were identified by UPLC-QToF/MS. The degradation pathway revealed differences among the four matrices; however hydroxylation, demethylation and cleavage reactions were observed in all matrices. To the best of our knowledge this is the first time that TMP degradation products have been identified by adopting a solar Fenton process at a pilot-scale set-up, using four different aqueous matrices., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The goal of this paper was to develop a modified photo-Fenton treatment able to degrade micro pollutants in municipal wastewater treatment plant (MWTP) effluents at a neutral pH with minimal iron and H(2)O(2) concentrations. Complexation of Fe by ethylenediamine-N,N'-disuccinic acid (EDDS) leads to stabilization and solubilization of Fe at natural pH. Photo-Fenton experiments were performed in a pilot compound parabolic collector (CPC) solar plant. Samples were treated with solid phase extraction (SPE) and analyzed by HPLC-Qtrap-MS. The rapid degradation of contaminants within the first minutes of illumination and the low detrimental impact on degradation of bicarbonates present in the water suggested that radical species other than HO(•) are responsible for the efficiency of such photo-Fenton process. Disinfection of MWTP effluents by the same process showed promising results, although disinfection was not complete.

Nowadays there is a continuously increasing worldwide concern for development of alternative water reuse technologies, mainly focused on agriculture and industry. In this context, Advanced Oxidation Processes (AOPs) are considered a highly competitive water treatment technology for the removal of those organic pollutants not treatable by conventional techniques due to their high chemical stability and/or low biodegradability. Although chemical oxidation for complete mineralization is usually expensive, its combination with a biological treatment is widely reported to reduce operating costs. This paper reviews recent research combining AOPs (as a pre-treatment or post-treatment stage) and bioremediation technologies for the decontamination of a wide range of synthetic and real industrial wastewater. Special emphasis is also placed on recent studies and large-scale combination schemes developed in Mediterranean countries for non-biodegradable wastewater treatment and reuse. The main conclusions arrived at from the overall assessment of the literature are that more work needs to be done on degradation kinetics and reactor modeling of the combined process, and also dynamics of the initial attack on primary contaminants and intermediate species generation. Furthermore, better economic models must be developed to estimate how the cost of this combined process varies with specific industrial wastewater characteristics, the overall decontamination efficiency and the relative cost of the AOP versus biological treatment., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Four biodegradability tests (Pseudomonas putida bioassay, Zahn-Wellens test, BOD5/COD ratio and respirometry assay) have been used to determine the biodegradability enhancement during the treatment of wastewater containing 200 mg L(-1) of dissolved organic carbon (DOC) of a five commercial pesticides mixture (Vydate, Metomur, Couraze, Ditumur and Scala) by an advanced oxidation process (AOP). A comparative study was carried out taking into account repeatability and precision of each biodegradability test. Solar photo-Fenton was the AOP selected for pesticide degradation up to three levels of mineralization: 20%, 40% and 60% of initial DOC. Intra- and interday precisions were evaluated conducting each biodegradability test by triplicate and they were applied three times on different dates over a period of three months. Fisher's least significant difference method was applied to the means, P. putida and Zahn-Wellens tests giving higher repeatability and precision. The P. putida test requires a shorter time to obtain reliable results using a standardized inoculum and constitutes a worthwhile alternative to estimate biodegradability in contrast to other less accurate or more time consuming methods., (Copyright (c) 2010 Elsevier Inc. All rights reserved.)

This work focuses on the treatment of real effluents from a municipal wastewater treatment plant (RE) with solar photo-Fenton (5 mg and 20 mg L(-1) Fe, pH approximately 3 and 50 mg L(-1) initial H(2)O(2) concentration) at pilot plant scale. In some experiments RE was spiked with 15 different (acetaminophen, antipyrine, atrazine, caffeine, carbamazepine, diclofenac, flumequine, hydroxybiphenyl, ibuprofen, isoproturon, ketorolac, ofloxacin, progesterone, sulfamethoxazole, and triclosan) emerging contaminants (ECs) at 100 and 5 microg L(-1) each which were added directly into RE prior to treatment. All experiments showed successful degradation of ECs in real effluents from different municipal wastewater treatment plants at low iron concentration (5 mg L(-1)). Although the most degradation took place during the Fenton process, photo-Fenton was necessary to degrade all ECs below their limit of detection (LOD). In the case of the RE containing 52 ECs (determined by HPLC-QTRAP-MS), four of them could not be degraded to their LOD and were still present, although at extremely low concentrations (nicotine 47 ng L(-1), cotinine 11 ng L(-1), chlorfenvinphos 99 ng L(-1), and caffeine 8 ng L(-1)). ECs were easily degraded by (*)OH without substantial competition with the organic content of the RE.

Remediation of pharmaceutical wastewater, containing nalidixic acid (NXA; 38 mg/L), a quinolone antibacterial agent commonly used in human and veterinary medicine, and characterized as having mainly 725 mg/L dissolved organic carbon (DOC), 3400 mg/L chemical oxygen demand, and around 4 g/L NaCl, was studied. A prior biodegradability study (Zahn-Wellens test) had demonstrated that the matrix was biodegradable after a rather long biomass adaptation period. After 4 days of treatment in an immobilized biomass reactor (IBR), 96% of the original DOC was removed by the biological treatment however, more than 50% of NXA was adsorbed on the biomass. As development of chronic toxicity in the IBR is possible after long exposure to NXA, adsorption and biomass stability during continuous exposure to NXA were studied in different cycles for one month. Afterthe biotreatment, the effluent was treated by solar photo-Fenton. Total degradation of NXA and reduction in toxicity were observed. The intermediates formed during degradation by biotreatment and subsequent photo-Fenton were studied by liquid chromatography-time-of-flight mass spectrometry.

Characterization and treatment of a real pharmaceutical wastewater containing 775 mg dissolved organic carbon per liter by a solar photo-Fenton/biotreatment were studied. There were also many inorganic compounds present in the matrix. The most important chemical in this wastewater was nalidixic acid (45 mg/L), an antibiotic pertaining to the quinolone group. A Zahn-Wellens test demonstrated that the real bulk organic content of the wastewater was biodegradable, but only after long biomass adaptation; however, the nalidixic acid concentration remained constant, showing that it cannot be biodegraded. An alternative is chemical oxidation (photo-Fenton process) first to enhance biodegradability, followed by a biological treatment (Immobilized Biomass Reactor--IBR). In this case, two studies of photo-Fenton treatment of the real wastewater were performed, one with an excess of H2O2 (kinetic study) and another with controlled H2O2 dosing (biodegradability and toxicity studies). In the kinetic study, nalidixic acid completely disappeared after 190 min. In the other experiment with controlled H2O2, nalidixic acid degradation was complete at 66 mM of H2O2 consumed. Biodegradability and toxicity bioassays showed that photo-Fenton should be performed until total degradation of nalidixic acid before coupling a biological treatment. Analysis of the average oxidation state (AOS) demonstrated the formation of more oxidized intermediates. With this information, the photo-Fenton treatment time (190 min) and H2O2 dose (66 mM) necessary for adequate biodegradability of the wastewater could be determined. An IBR operated in batch mode was able to reduce the remaining DOC to less than 35 mg/L. Ammonium consumption and NO3- generation demonstrated that nitrification was also attained in the IBR. Overall DOC degradation efficiency of the combined photo-Fenton and biological treatment was over 95%, of which 33% correspond to the solar photochemical process and 62% to the biological treatment.

Two advanced oxidation processes (AOPs), ozonation and photo-Fenton, combined with a pilot aerobic biological reactor at field scale were employed for the treatment of industrial non-biodegradable saline wastewater (TOC around 200 mgL(-1)) containing a biorecalcitrant compound, alpha-methylphenylglycine (MPG), at a concentration of 500 mgL(-1). Ozonation experiments were performed in a 50-L reactor with constant inlet ozone of 21.9 g m(-3). Solar photo-Fenton tests were carried out in a 75-L pilot plant made up of four compound parabolic collector (CPC) units. The catalyst concentration employed in this system was 20 mgL(-1) of Fe2+ and the H2O2 concentration was kept in the range of 200-500mgL(-1). Complete degradation of MPG was attained after 1,020 min of ozone treatment, while only 195 min were required for photo-Fenton. Samples from different stages of both AOPs were taken for Zahn-Wellens biocompatibility tests. Biodegradability enhancement of the industrial saline wastewater was confirmed (>70% biodegradability). Biodegradable compounds generated during the preliminary oxidative processes were biologically mineralised in a 170-L aerobic immobilised biomass reactor (IBR). The global efficiency of both AOP/biological combined systems was 90% removal of an initial TOC of over 500 mgL(-1).

Aqueous solutions of a mixture of several pesticides (alachlor, atrazine, chlorfenvinphos, diuron and isoproturon), considered PS (priority substances) by the European Commission, and an intermediate product of the pharmaceutical industry (alpha-methylphenylglycine, MPG) chosen as a model industrial pollutant, have been degraded at pilot-plant scale using ozonation. This study is part of a large research project [CADOX Project, A Coupled Advanced Oxidation-Biological Process for Recycling of Industrial Wastewater Containing Persistent Organic Contaminants, Contract No.: EVK1-CT-2002-00122, European Commission, http://www.psa.es/webeng/projects/cadox/index.html] founded by the European Union that inquires into the potential coupling between chemical and biological oxidations for the removal of toxic or non-biodegradable contaminants from water. The evolution of pollutant concentration, TOC mineralization, generation of inorganic species and consumption of O3 have been followed in order to visualize the chemical treatment effectiveness. Although complete mineralization is hard to accomplish, and large amounts of the oxidant are required to lower the organic content of the solutions, the possibility of ozonation cannot be ruled out if partial degradation is the final goal wanted. In this sense, Zahn-Wellens biodegradability tests of the ozonated MPG solutions have been performed, and the possibility of a further coupling with a secondary biological treatment for complete organic removal is envisaged.

A comparative life cycle assessment (LCA) of two solar-driven advanced oxidation processes, namely heterogeneous semiconductor photocatalysis and homogeneous photo-Fenton, both coupled to biological treatment, is carried out in order to identify the environmentally preferable alternative to treat industrial wastewaters containing non-biodegradable priority hazardous substances. The study is based on solar pilot plant tests using alpha-methyl-phenylglycine as a target substance. The LCA study is based on the experimental results obtained, along with data from an industrial-scale plant. The system under study includes production of the plant infrastructure, chemicals, electricity, transport of all these materials to the plant site, management of the spent catalyst by transport and landfilling, as well as treatment of the biodegradable effluent obtained in a conventional municipal wastewater treatment plant, and excess sludge treatment by incineration. Nine environmental impact categories are included in the LCA: global warming, ozone depletion, human toxicity, freshwater aquatic toxicity, photochemical ozone formation, acidification, eutrophication, energy consumption, and land use. The experimental results obtained in the pilot plant show that solar photo-Fenton is able to obtain a biodegradable effluent much faster than solar heterogeneous photocatalysis, implying that the latter would require a much larger solar collector area in an industrial application. The results of the LCA show that, an industrial wastewater treatment plant based on heterogeneous photocatalysis involves a higher environmental impact than the photo-Fenton alternative, which displays impact scores 80-90% lower in most impact categories assessed. These results are mainly due to the larger size of the solar collector field needed by the plant.

Photo-Fenton/ozone (PhFO) and TiO2-photocatalysis/ozone (PhCO) coupled systems are used as advanced oxidation processes for the degradation of the following biorecalcitrant pesticides: alachlor, atrazine, chlorfenvinfos, diuron, isoproturon and pentachlorophenol. These organic compounds are considered Priority Hazardous Substances by the Water Framework Directive of the European Commission. The degradation process of the different pesticides, that occurs through oxidation of the organic molecules by means of their reaction with generated OH radical, follows a first and zero-order kinetics, when PhFO and PhCO are applied, respectively. These two Advanced Oxidation Processes, together with the traditional ozone+UV, have been used to investigate TOC reduction of the different pesticide aqueous solutions. The best results of pesticide mineralization are obtained when PhFO is applied; with the use of this advanced oxidation process the aqueous pesticide solutions become detoxyfied except in the case of atrazine and alachlor aqueous solutions for which no detoxification is achieved at the experimental conditions used in the work, at least after 2 and 3 h of treatment, respectively.

The photocatalytic organic content reduction of a selected synthetic municipal wastewater by the use of heterogeneous and homogeneous photocatalytic methods under solar irradiation has been studied at a pilot-plant scale at the Plataforma Solar de Almeria. In the case of heterogeneous photocatalysis the effect of catalysts and oxidants concentration on the decomposition degree of the wastewater was examined. By an accumulation energy of 50 kJL(-1) the synergetic effect of 0.2 gL(-1)TiO(2) P-25 with hydrogen peroxide (H(2)O(2)) and Na(2)S(2)O(8) leads to a 55% and 73% reduction of the initial organic carbon content, respectively. The photo-fenton process appears to be more efficient for this type of wastewater in comparison to the TiO(2)/oxidant system. An accumulation energy of 20 kJL(-1) leads to 80% reduction of the organic content. The presence of oxalate in the Fe(3+)/H(2)O(2) system leads to an additional improvement of the photocatalytic efficiency.

TiO2-catalyst suspensions work efficiently in photocatalysis for wastewater treatment. Nevertheless, once photocatalysis is complete, separation of the catalyst from solution becomes the main problem. Catalyst recovery has been enhanced through charge neutralisation and coagulation with electrolytes at lab and pilot-plant scale (40 L) to evaluate the potential for its separation after photocatalytic degradation of pollutants. Zeta-potential analysis showed that the isoelectric point (IEP) of TiO2 suspensions is near pH 7. Settling rates and hydrodynamic diameter of TiO2 particles are maximum at the IEP. However, suspensions are stable at different pH. TiO2 was reused in solar photocatalysis pilot-plant (40 L) for treatment of tetrachloroethylene (C2Cl4) comparing two procedures: reuse of the entire suspension after destruction of the organics without separation of the catalyst, and reuse of the catalyst after it had settled to the bottom and clear water had been removed. Photocatalytic efficiency worsens with successive runs when catalyst and water are reused without separation, whereas, when TiO2 is separated, the photocatalyst is not deactivated.

The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solutions has been investigated under solar irradiation in the compound parabolic collector reactor at Plataforma Solar de Almeria. Hydroxyl radicals *OH, responsible of the degradation, are formed via an intramolecular photoredox process in the excited state of Fe(III) aquacomplexes. The primary step of the reaction is mainly due to the attack of *OH radicals on the aromatic ring. For prolonged irradiations DEP and its photoproducts are completely mineralized due to the regeneration of the absorbing species and the continuous formation of *OH radicals that confers a catalytic aspect to the process. Consequently, the degradation photoinduced by Fe(III) could be an efficient method of DEP removal from water.

The technical feasibility and performance of photocatalytic degradation of aqueous methomyl (50 mg/L) have been studied at pilot scale in two well-defined systems of special interest because natural-solar UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. The pilot plant is made up of compound parabolic collectors specially designed for solar photocatalytic applications. Experimental conditions allowed pesticide disappearance, degree of mineralisation and toxicity achieved in the two photocatalytic systems to be compared. Total disappearance of methomyl is attained by photo-Fenton in 60 min and by TiO2 in 100 min. Hundred percent of nitrogen and sulphur are recovered as ammonium and sulphate. By contrast, complete mineralisation of total organic carbon (TOC) is not achieved even after quite a long time (more than 300 min). Three different bioassays (Vibrio fischeri, Daphnia magna and a Microalga) have been used for testing the progress of toxicity during treatment. All remained toxic down to very low-pesticide concentrations and in some bioassays were still toxic after total disappearance of the pesticide. Only if treatment is maintained throughout enough mineralisation (i.e. TOC disappearance), the toxicity is reduced to below the threshold (EC50%).

The photocatalytic degradation of various toxic organic compounds has been proposed as a viable process to detoxify drinking water. Irradiating pulverulent semi-conductors like TiO2 in suspension or fixed to various supports in aqueous solutions containing organic pollutants, creates a redox environment able to destroy these pollutants. Solar photocatalytic mineralization of organic water pollutants has a strong potential in the industrial destruction of toxic organics in water as this has been widely demonstrated in recent years, and the applications and target compounds are numerous. The aim of this paper is to present the basic principle of the photocatalysis and especially to show the various applications of the solar photocatalysis in the field of the decontamination of wastewater.

A European industrial consortium called SOLARDETOX has been created as the result of an EC-DGXII BRITE-EURAM-III-financed project on solar photocatalytic detoxification of water. The project objective was to develop a simple, efficient and commercially competitive water-treatment technology, based on compound parabolic collectors (CPCs) solar collectors and TiO2 photocatalysis, to make possible easy design and installation. The design, set-up and preliminary results of the main project deliverable, the first European industrial solar detoxification treatment plant, is presented. This plant has been designed for the batch treatment of 2 m3 of water with a 100 m2 collector-aperture area and aqueous aerated suspensions of polycrystalline TiO2 irradiated by sunlight. Fully automatic control reduces operation and maintenance manpower. Plant behaviour has been compared (using dichloroacetic acid and cyanide at 50 mg l(-1) initial concentration as model compounds) with the small CPC pilot plants installed at the Plataforma Solar de Almería several years ago. The first results with high-content cyanide (1 g l(-1)) waste water are presented and plant treatment capacity is calculated.

The photodegradation of isoproturon (IP) was performed using TiO2 supported on glass rings in a 1.5 l coaxial rector. After 60 min of phototreatment, IP was completely eliminated and about 80% of dissolved organic carbon (DOC) remained in solution. This efficiency of photodegradation was compared with that using the suspended catalyst in solution and the results indicated that the catalytic activity of TiO2 is not reduced when it is immobilized. The durability of the supported TiO2 was also tested. It was found that after 300 h of photodegradation experiments, its activity was not affected. The chemical nature of the phototreated solution was assessed following the evolution of the initial compound, the organic carbon, and the formed ions, as well as the toxicity and the biodegradability. These analyses demonstrated that the solution resulting from the phototreatment of IP is biologically compatible and its complete mineralization can be performed by biological means. In this way, for the mineralization of an IP solution, a combined photochemical and biological flow reactor was used operating in semi-continuous mode at laboratory scale. This coupled system employs TiO2 supported on glass rings in the photocatalytic reactor and bacteria supported on biolite in the biological part. In this combined system, 100% of the initial concentration of IP and 95% of DOC were removed. Finally, some field experiments under direct sunlight were carried out at the Plataforma Solar de Almerı´a (PSA), Spain. The photocatalytic oxidation of IP was performed in homogeneous and heterogeneous solutions and two different reactors were compared: a medium concentrating radiation system (Helioman, HM) and a non-concentrating radiation system (compound parabolic collectors, CPC). The degradation rates obtained in the CPC are around 5 times more efficient than the HM collectors. However, in both systems 100% of the initial concentration of IP was removed. The possibility of coupling a CPC photoreactor with a biological system at field pilot scale employing supported TiO2 and fixed bacteria for the treatment of real bio-recalcitrant wastewater is also suggested. [Copyright &y& Elsevier]

Abstract: Growing use of xenobiotic substances, synthetic fragrances, pesticides, drugs, and other contaminants is leading to their increasing concentrations in the aquatic environment (over 1μg/L). Conventional municipal wastewater treatment plants (MWTP) are unable to degrade these contaminants entirely. In this study, solar photo-Fenton process is proposed and optimized as a tertiary treatment for MWTP effluents containing emerging contaminants (ECs) and other micro-pollutants. A three-level factorial experimental design (33), modified with 2×3 axial and 6 central runs to make it spherical was carried out for optimization using Statgraphics software. The influence of hydrogen peroxide dosage, iron (II) concentration and temperature were assessed over accumulated energy (Q UV kJ/L as the response factor) necessary to remove more than 95% of the micro-pollutants. Pareto graphic and response surfaces showed that Fe (II) concentration, temperature and their interaction are the variables that influence the response factor the most. Finally, the optimal operating conditions were successfully applied to the treatment of a real MWTP effluent at pilot plant scale removing 80% of total micropollutants after 0.56kJ/L. [Copyright &y& Elsevier]