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To shorten phototreatment time is of major concern for the cost and energy benefits of the xenobiotics degradation performed by photocatalytic processes. Using photo-Fenton and TiO2 phototreatments, partially photodegraded solutions of 6 separate pesticides (alachlor, atrazine, chlorfenvinphos, diuron, isoproturon and pentachlorophenol) were tested for biocompatibility, which was evaluated according to the Zahn–Wellens procedure. This study investigated if Microtox© could be considered as a suitable global indicator capable of giving information on the evolution of biocompatibility of the water solution contaminated with organic pollutants during the phototreatment in order to promote biotreatment. The obtained results demonstrated that biodegradability increased significantly after short photo-Fenton treatment times for alachlor, diuron and pentachlorophenol. Uncertain results were obtained with atrazine and isoproturon. Microtox© acute toxicity testing was shown to correctly represent dynamics and efficiency of phototreatment. [Copyright &y& Elsevier]

This work assessed the solar photo-Fenton degradation of nalidixic acid (NXA), a quinolone antibacterial agent, in several different aqueous solutions. It has been proven that the composition of the water clearly affects the efficiency of the photo-Fenton process. The presence of chlorine ions induces the concurrence of different mechanisms involving Cl· and Cl2·- radicals, which slow down the process. Up to 35 transformation products (TPs) were identified and their structures characterized by accurate LC–TOF-MS mass measurements during treatment of the different model waters. Photocatalytic degradation was thus observed to proceed mainly through the attack of the hydroxyl radicals on the double bond C(2)=C(3) which induce further ring opening. All the TPs identified persisted after total degradation of NXA. NXA in real pharmaceutical effluent was treated by photo-Fenton as a first stage before biological treatment. As NXA has been demonstrated to be recalcitrant to biological treatment, photo-Fenton treatment of the effluent was continued until its total degradation. Although NXA was efficiently degraded, LC–MS analyses demonstrated that some of the TPs identified after the photo-Fenton treatment were also recalcitrant to biological treatment, persisting after the combined treatment. These results show that analytical assessment of photocatalytic water treatments is essential to assure they are functioning as intended. [ABSTRACT FROM AUTHOR]

Abstract: Direct photolysis and solar TiO2 photocatalysis of Trimethoprim (TMP) in different water matrices (demineralised and simulated seawater) have been studied. Direct photolysis yielded a similar, slow TMP degradation rate in both water matrices, and the formation of very stable photo-transformation products. Dissolved organic carbon decreased slightly after prolonged irradiation. The main intermediate identified was a ketone derivative (trimethoxybenzoylpyrimidine), which was proved to be a photosensitizer of TMP degradation. During TiO2 photocatalysis, TMP was completely eliminated in both water matrices at a similar rate, however, the mineralization rate was appreciably reduced in seawater, which can be explained by the presence of inorganic species acting as hydroxyl radical scavengers, and directly affecting photocatalytic efficiency. Identification of intermediates showed differences between the two processes but hydroxylation, demethylation and cleavage of the original drug molecule were observed in both. [Copyright &y& Elsevier]

Abstract: A multivariate analysis using experimental design techniques was performed to determine the effect of iron, hydrogen peroxide and titanium dioxide in the solar photodegradation of dichloroacetic acid in a combined TiO2/photo-Fenton process. The study was carried out at pilot-plant scale, using TiO2 supported on silica as the heterogeneous photocatalyst to facilitate separation of the solids after the reaction, and iron concentrations of less than 3mgL−1 to avoid removal of iron from the effluent. The results show that iron is the most important factor influencing the reaction rate, which suggests that in strongly acidic solutions, the Fenton mechanism controls the process even at such low iron concentrations. Under these conditions, the expected synergism between TiO2 and iron degradation pathways seems to be negligible compared to the antagonistic effect between hydrogen peroxide and TiO2, which reduces the activity of the combined system. However, in the absence of hydrogen peroxide, the activity achieved by the combined Fe/TiO2 system is similar to that of the photo-Fenton process, with the advantage that H2O2 is replaced by a reusable TiO2-based catalytic material. Consequently, the analysis of pilot-plant operation economics took not only the degradation rate, but also the cost of chemicals into account. [Copyright &y& Elsevier]

Abstract Urban wastewater treatment plants (WWTPs) are among the main anthropogenic sources for the release of contaminants of emerging concern (CECs) into the environment, which can result in toxic and adverse effects on aquatic organisms and consequently on humans. Unfortunately, WWTPs are not designed to remove CECs and secondary (e.g., conventional activated sludge process, CAS) and tertiary (such as filtration and disinfection) treatments are not effective in the removal of most CECs entering WWTP. Accordingly, several advanced treatment methods have been investigated for the removal of CECs from wastewater, including consolidated (namely, activated carbon (AC) adsorption, ozonation and membranes) and new (such as advanced oxidation processes (AOPs)) processes/technologies. This review paper gathers the efforts of a group of international experts, members of the NEREUS COST Action ES1403 who for three years have been constructively discussing the state of the art and the best available technologies for the advanced treatment of urban wastewater. In particular, this work critically reviews the papers available in scientific literature on consolidated (ozonation, AC and membranes) and new advanced treatment methods (mainly AOPs) to analyse: (i) their efficiency in the removal of CECs from wastewater, (ii) advantages and drawbacks, (iii) possible obstacles to the application of AOPs, (iv) technological limitations and mid to long-term perspectives for the application of heterogeneous processes, and (v) a technical and economic comparison among the different processes/technologies. Graphical abstract Unlabelled Image Highlights • Adsorption, O 3 , NF and RO membranes filtration can effectively remove CECs. • (Solar driven) AOPs appear competitive for CECs removal from urban wastewater. • When applying O 3 or AOPs ecotoxicological studies should be performed. • Lack of comparative investigations between consolidated and new processes • Conclusive evaluation of the most suitable and cost effective solution/s not yet possible [ABSTRACT FROM AUTHOR]

This paper reports on the combined solar photo-Fenton/biological treatment of an industrial effluent (initial total organic carbon, TOC, around 500mgL−1) containing a non-biodegradable organic substance (α-methylphenylglycine at 500mgL−1), focusing on pilot plant tests performed for design of an industrial plant, the design itself and the plant layout. Pilot plant tests have demonstrated that biodegradability enhancement is closely related to disappearance of the parent compound, for which a certain illumination time and hydrogen peroxide consumption are required, working at pH 2.8 and adding Fe2+ =20mgL−1. Based on pilot plant results, an industrial plant with 100m2 of CPC collectors for a 250L/h treatment capacity has been designed. The solar system discharges the wastewater (WW) pre-treated by photo-Fenton into a biotreatment based on an immobilized biomass reactor. First, results of the industrial plant are also presented, demonstrating that it is able to treat up to 500Lh−1 at an average solar ultraviolet radiation of 22.9Wm−2, under the same conditions (pH, hydrogen peroxide consumption) tested in the pilot plant. [Copyright &y& Elsevier]

Abstract: In recent years, there has been a tremendous amount of research and development in the area of photocatalysis, a process included in a special class of oxidation techniques defined as advanced oxidation processes (AOPs), all characterized by the same chemical feature, production of ls. This paper reviews the use of sunlight to produce the ls. The systems necessary for performing solar photocatalysis are described. The paper also summarizes most of the research related to solar photocatalytic degradation of water contaminants carried out during recent years, and how it could significantly contribute to the treatment of very persistent toxic compounds. Various solar reactors for photocatalytic water treatment based mainly on non-concentrating collectors erected during the last few years are also described in detail in this review, as well as the use of the solar photocatalytic processes to inactivate microorganisms present in water, placing special emphasis on some experimental systems erected to optimize this disinfecting technique. [Copyright &y& Elsevier]

Abstract: Alachlor, atrazine and diuron dissolved in water at 50, 25 and 30mg/L, respectively were photodegraded by Fe2+/H2O2, Fe3+/H2O2, TiO2 and TiO2/Na2S2O8 treatments driven by solar energy at pilot-plant scale using a compound parabolic collector (CPC) photoreactor. All the advanced oxidation processes (AOPs) employed mainly compared the TOC mineralisation rate to evaluate treatment effectiveness. Parent compound disappearance, anion release and oxidant consumption are discussed as a function of treatment time. The use of Fe2+ or Fe3+ showed no influence on the reaction rate under illumination and the reaction using 10 or 55mg/L of iron was quite similar. TiO2/Na2S2O8 showed a quicker reaction rate than TiO2 and a similar rate compared to photo-Fenton. The main difference found was between TiO2/Na2S2O8 and photo-Fenton, detected during atrazine degradation, where pesticide transformation into cyanuric acid was confirmed only for TiO2/Na2S2O8. [Copyright &y& Elsevier]

Abstract: In this paper, we present the photo-Fenton treatment in a solar pilot-plant scale of several EU priority hazardous substances (Alachlor, Atrazine, Chlorfenvinphos, Diuron and Isoproturon) dissolved in water. The results have been evaluated not only from the point of view of contaminant disappearance and mineralisation, but also of toxicity reduction and enhancement of biodegradability. Degradation was monitored by total organic carbon, pesticide concentration by HPLC–UV, inorganics released by ion chromatography, and biodegradability by the Zahn–Wellens (Z–W) test. The total volume of the solar photoreactor, composed of compound parabolic collectors with a total area of 4.16m2, was between 70 and 82L. The treatment was shown to be effective, mineralising all of the pesticides tested, both alone and in mixtures. In order to find out the conditions for biocompatibility using the photo-Fenton reaction as a pre-treatment step, wastewater inoculated with unacclimated municipal sludge containing pesticides after certain degradation time was evaluated by the Z–W test. Biodegradability was enhanced (70% considered biodegradable) by the photo-Fenton treatment after 12–25min. It may be concluded that the photo-Fenton treatment consistently enhances biodegradability of wastewater containing pesticides. [Copyright &y& Elsevier]

The technical feasibility and performance of photocatalytic degradation of four water-soluble pesticides (diuron, imidacloprid, formetanate and methomyl) have been studied at pilot scale in two well-defined systems which are of special interest because natural-solar UV light can be used for them: 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. The initial concentration tested with imidacloprid, formetanate and methomyl was 50 and 30 mg/l with diuron, and the catalyst concentrations were 200 mg/l and 0.05 mM with TiO2 and iron, respectively. Total disappearance of the parent compounds, 90% mineralisation and toxicity reduction below the threshold (EC50) have been attained with all pesticides tested. All these results have contributed to an evaluation of photocatalytic treatment capacity and comments on the main parameters of TiO2 and Fe separation from the treated water. [Copyright &y& Elsevier]