Practical approach to the evaluation of industrial wastewater treatment by the application of advanced microbiological techniques.

In cork industry, the operation of boiling raw cork generates large volumes of wastewater named Cork Boiling Wastewater (CBW). The main characteristics are the low biodegradability and medium to low acute toxicity, resulting in the necessity of designing advanced biological treatments by possible conventional activated sludge adaptation. In order to evaluate the variation of bacterial population along that process, a study based on optical microscopy, plate count, DNA extraction, qPCR and massive sequencing techniques was performed. Results showed a diminution of the total and volatile solids (TSS and VSS), jointly with a decrease in DNA concentration, general bacteria (16 S) and ammonia-oxidizing bacteria (AOB). After a few hours of testing, diverse microbiological species died while others showed a possible adaptation of the biological system, accompained by a dissolved organic carbon (DOC) reduction. In addition, toxicity tests based on activated sludge showed the development of chronic toxicity through the contact time. Combination of classical and advanced microbiological techniques, such as quantitative real time Polymerase Chain Reaction (qPCR) and metagenomics, was essential to predict the variation of species during the experiment and to conclude if effective biological adaptation could be finally attained for the target complex wastewater.

Removal of microcontaminants by zero-valent iron solar processes at natural pH: Water matrix and oxidant agents effect.

This work deals with microcontaminants (MCs) removal by natural solar zero-valent iron (ZVI) process at natural pH in actual matrices. Commercial ZVI microspheres were selected as ZVI source and hydrogen peroxide and persulfate were used as oxidant agents. The experimental plan comprised the evaluation of sulphates and carbonates/bicarbonates effect on process performance, the possibility of adding an iron chelate (EDDS) to take advantage of leached iron and the treatment of MCs in actual MWWTP secondary effluent. The presence of sulphates and EDDS addition did not lead to significant changes in the process efficiency, while the carbonates naturally present in natural water (458 mg/L) diminished the treatment time need to reach the decontamination goal. Finally, the treatment of a MCs mixture consisting of Atrazine, Carbendazim, Imidacloprid, and Thiamethoxam in the range of µg/L in actual MWWTP secondary effluent by solar/msZVI/H2O2 and solar/msZVI/S2O82- obtained 7 and 22% of total removal after 180 min, respectively, which indicated a moderate competitiveness of these processes with respect to other advanced oxidation processes.

Evaluation of commercial zerovalent iron sources in combination with solar energy to remove microcontaminants from natural water at circumneutral pH.

Solar zerovalent iron (ZVI) was studied at circumneutral pH in combination with hydrogen peroxide and persulfate for removal of imidacloprid as a model contaminant in natural water. Three commercial ZVI sources, steel wool (ZVI-SW) and two iron micro-powders (ZVI-MS and ZVI-S) were independently evaluated. First, different ZVI corrosion conditions were tested in contact with air, exposed to natural solar radiation and with addition of oxidants, such as H2O2 and S2O82-, demonstrating the importance of released iron. Then, the technical feasibilities of solar/H2O2/ZVI and solar/S2O82-/ZVI were assessed for the elimination of 1 mg/L of imidacloprid. In general, H2O2 concentrations and treatment times were high. Only ZVI-MS (1 mM) reached 80% imidacloprid degradation after 157 min and 3 mM (102 mg/L) of H2O2. Solar/S2O82-/ZVI performance was better, reaching >80% imidacloprid degradation in <60 min with 1 mM (192 mg/L) S2O82- for all ZVI sources. Efficiency was highest with ZVI-MS, which was therefore selected for feasibility testing of a microcontaminant (MC) mixture containing 100 µg/L each of atrazine, carbendazim, imidacloprid and thiamethoxam with both solar/oxidizing agents/ZVI. H2O2 took 180 min to achieve 76% degradation of the sum of MCs, while 80% total degradation was reached after 69 min by adding S2O82-, confirming its higher efficiency. Finally, this study showed that ZVI in combination with solar radiation does not enhance significantly the photocatalytic cycle.

Solar photo-assisted electrochemical processes applied to actual industrial and urban wastewaters: A practical approach based on recent literature.

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 Fe2+ 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.

Carbon-based cathodes degradation during electro-Fenton treatment at pilot scale: Changes in H2O2 electrogeneration.

Autopsy of carbon-PTFE cathodes was performed by addressing their degradation in a commercial plate-and-frame cell equipped with a Nb-BDD anode. Cell is arranged within an electrochemical pilot plant designed for treating wastewaters by electrochemical Fenton-like processes, thus an efficient electrocatalytic production of H2O2 is necessary to guarantee Fenton's reaction. Significant decrease in H2O2 electrogeneration occurred during pilot plant operation, hindering the efficient performance of Fenton-like processes. Two cathodes were studied, first was operated at pH 3 and second at neutral pH by using EDDS as complexing agent to maintain iron in solution. Electrogenerated H2O2 decreased from 43 mg L-1 to 16 mg L-1 in the first cathode after 50 h of operation and from 49 mg L-1 to 24 mg L-1 in the second one after 26 h of operation. Both were cleaned with 30% (v/v) solution of HCl/water for 24 h and H2O2 production was recovered only in the second cathode (able to generate 39 mg L-1). Autopsy of the cathodes was tackled by scanning electron microscopy (SEM) and X-ray energy dispersive (EDX), evidencing a strong degradation of first cathode surface and iron oxide inlays in second one due to the decomposition of Fe3+:EDDS and consequent iron precipitation at neutral pH.

A comparative study of different tests for biodegradability enhancement determination during AOP treatment of recalcitrant toxic aqueous solutions.

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.

Electro-oxidation process assisted by solar energy for the treatment of wastewater with high salinity.

Industrial wastewaters characterized by its high content in organics and conductivity entails a challenge for conventional treatments due to its low biodegradability. Electro-oxidative processes have been successfully applied for the treatment of this kind of wastewaters achieving high organics and ammonia removal. The degradation process is executed mainly by electrochemically generated active chlorine species, as HClO and ClO- with E0 = 1.49 V; and E0 = 0.89 V, respectively. Under solar radiation, specifically at 313 nm, the formation of Cl (E0 = 2.4 V) from ClO- is promoted, improving the oxidizing capacity of the process. In this work the combination of an electrochemical device with a solar photo-reactor has been evaluated aiming to increase the degradation rate per kWh-1. Two different complex industrial wastewaters were tested, achieving higher organics degradation when electrochemical treatment was assisted by solar light. Toxicity reduction was also assessed and biodegradability enhanced and allowing its ulterior lower-cost biological treatment.

Advanced evaluation of landfill leachate treatments by low and high-resolution mass spectrometry focusing on microcontaminant removal.

Conventional wastewater treatments are not usually effective in the remediation of specific landfill leachates due to their high content in toxic and recalcitrant compounds. Advanced and intensive treatments are needed for the decontamination and possible recycling of these effluents. Here, the combination of advanced oxidation processes (solar photo-Fenton) and an aerobic biological reactor have been applied to treat urban landfill leachates. The effectiveness of the proposed treatment line was also evaluated considering the removal of organic microcontaminants (OMCs) identified in the different phases, which is an innovative practice. The analytical strategy included: (i) a target approach (115 analytes) by liquid chromatography-mass spectrometry (LC-MS/MS); and two suspect approaches using (ii) LC-high-resolution MS (database with >1300 compounds) and (iii) gas-chromatography-MS (database with >900 compounds). OMCs on the treated landfill leachate was reduced up to 94% of the initial concentration. 8 target compounds (mainly pharmaceuticals) out of 115 target analytes represented 85% of the OMC concentration in the raw leachate: cotinine, diclofenac, gabapentin, ketoprofen, lidocaine, mecoprop, nicotine and trigonelline. 3 non-previously reported OMCs were confirmed: di-n-nonyl phthalate, o-phenylphenol and tonalide. Leachate partially oxidized by solar photo-Fenton process can be successfully incorporated to biological systems to complete the treatment by means of specifically adapted biomass.

Solar photocatalytic degradation of pesticides over TiO2-rGO nanocomposites at pilot plant scale.

Two TiO2-rGO nanocomposites were prepared by hydrothermal method from commercial TiO2 (P25 and Hombikat UV100, HBK). In both cases TiO2 nanoparticles appeared intimate and homogeneously distributed on rGO surface, but forming a dense network in P25-rGO nanocomposite, and a more open structure in HBK-rGO. Zeta potential and particle size distribution favored the ease of HBK-rGO nanocomposite to form stable suspensions. A comparative analysis of these two photocatalysts was performed on the pilot plant scale solar assisted photodegradation of a 200 µg·L-1 or 5 mg·L-1 mixture of persistent and biorecalcitrant pollutants in deionized water (methomyl, pyrimethanil, isoproturon and alachlor, all used as pesticides). Complete removal of pesticides was achieved, though faster with P25-rGO when O2 was the oxidant. However, the use of hydrogen peroxide (H2O2) dosage as oxidant speeded up pesticides removal, but HBK-rGO performance resulted much improved. Finally, at realistic very low concentrations of 200 µgeach pesticide·L-1, the complete removal of pesticides was achieved at very short times (<25 min), showing the efficiency of the synthetized TiO2-rGO nanocomposites in this pilot-plat scale solar process to mitigate refractory and biorecalcitrant contaminants on effluents as a sustainable and efficient process.

Decontamination industrial pharmaceutical wastewater by combining solar photo-Fenton and biological treatment.

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.

A reliable monitoring of the biocompatibility of an effluent along an oxidative pre-treatment by sequential bioassays and chemical analyses.

A new approach to assess biocompatibility of an effluent, based on combination of different bioassays and chemical analyses, has been tested using a mixture of four commercial pesticides treated by a solar photo-Fenton as target effluent. A very fast elimination of the pesticides occurred (all of them were below detection limit at t30W=36 min), but mineralisation was a more time-consuming process, due to the formation of organic intermediates and to the presence of solvents, as shown by GC-MS analysis. Measurements based on activated sludge indicated that detoxification was coincident with the removal of the active ingredients, while more sensitive Vibrio fischeri bacterium showed significant toxicity until the end of the experiment, although the effluent might be compatible with biological processes. Biodegradability of the solutions was enhanced by the photochemical process, to reach BOD5/COD ratios above 0.8. Longer time bioassays, such as the Zahn-Wellens' test, support the applicability of coupling photochemical with activated sludge-based biological processes to deal with these effluents.

Confirming Pseudomonas putida as a reliable bioassay for demonstrating biocompatibility enhancement by solar photo-oxidative processes of a biorecalcitrant effluent.

Experiments based on Vibrio fischeri, activated sludge and Pseudomonas putida have been employed to check variation in the biocompatibility of an aqueous solution of a commercial pesticide, along solar photo-oxidative process (TiO(2) and Fenton reagent). Activated sludge-based experiments have demonstrated a complete detoxification of the solution, although important toxicity is still detected according to the more sensitive V. fischeri assays. In parallel, the biodegradability of organic matter is strongly enhanced, with BOD(5)/COD ratio above 0.8. Bioassays run with P. putida have given similar trends, remarking the convenience of using P. putida culture as a reliable and reproducible method for assessing both toxicity and biodegradability, as a substitute to other more time consuming methods.

Microbiological evaluation of combined advanced chemical-biological oxidation technologies for the treatment of cork boiling wastewater.

This paper contains a multidisciplinary approach that will contribute to design and properly evaluate a treatment line for complex biorecalcitrant wastewaters. To demonstrate this approach a specific industrial wastewater (cork boiling wastewater, CBW) was used. A treatment line based on a coagulation-flocculation step followed by an Advanced Oxidation Process (AOP) (solar photo-Fenton) and combined with an aerobic biological system was evaluated. Applied microbiological techniques: optical microscopy, plate count, DNA extraction and qPCR, indicated that some communities disappeared after the activated sludge adaptation period to the partially treated wastewater, while communities that did not disappear were damaged: 2-log reduction of total heterotrophic bacteria (THB) and a decrease in DNA concentration from 200 ng/µL to 65 ng/µL were observed. Therefore, chemical and microbiological results obtained along the set of experiments, suggested the inefficiency of the combined treatment option between solar photo-Fenton and advanced aerobic biological systems for CBW. This led to the necessity of applying solar photo-Fenton without combining with biotreatment and with the objective of improving the effluent quality enough for being reused in the own industry. Toxicity tests, based on different organisms (after coagulation-flocculation followed by solar photo-Fenton), showed increase on acute toxicity (from 46% to 71% by respirometric assays) and the development of chronic toxicity (from 21-29% to 83-90% also measured by respirometric assays), made evident the incompatibility of this type of wastewater with a biological treatment even after the application of an AOP.

Photo-Fenton treatment of saccharin in a solar pilot compound parabolic collector: Use of olive mill wastewater as iron chelating agent, preliminary results.

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 H2O2 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.

EDDS as complexing agent for enhancing solar advanced oxidation processes in natural water: Effect of iron species and different oxidants.

The main purpose of this pilot plant study was to compare degradation of five microcontaminants (MCs) (antipyrine, carbamazepine, caffeine, ciprofloxacin and sulfamethoxazole at 100 µg/L) by solar photo-Fenton mediated by EDDS and solar/Fe:EDDS/S2O82-. The effects of the Fe:EDDS ratio (1:1 and 1:2), initial iron species (Fe(II) or Fe(III) at 0.1 mM) and oxidizing agent (S2O82- or H2O2 at 0.25-1.5 mM) were evaluated. The higher the S2O82- concentration, the faster MC degradation was, with S2O82- consumption always below 0.6 mM and similar degradation rates with Fe(II) and Fe(III). Under the best conditions (Fe 0.1 mM, Fe:EDDS 1:1, S2O82- 1 mM) antipyrine, carbamazepine, caffeine, ciprofloxacin and sulfamethoxazole at 100 µg/L where 90% eliminated applying a solar energy of 2 kJ/L (13 min at 30 W/m2 solar radiation <400 nm). Therefore, S2O82- promotes lower consumption of EDDS as Fe:EDDS 1:1 was better than Fe:EDDS 1:2. In photo-Fenton-like processes at circumneutral pH, EDDS with S2O82- is an alternative to H2O2 as an oxidizing agent.

Photodegradation of malachite green under natural sunlight irradiation: kinetic and toxicity of the transformation products.

This article describes the photolytic degradation of malachite green (MG), a cationic triphenylmethane dye used worldwide as a fungicide and antiseptic in the aquaculture industry. Photolysis experiments were performed by direct exposure of a solution of MG in water to natural sunlight. The main transformation products (TPs) generated during the process were identified by liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) and gas chromatography mass spectrometry (GC-MS). The 28 TPs identified with this strategy indicate that MG undergoes three main reactions, N-demethylation, hydroxylation and cleavage of the conjugated structure forming benzophenone derivatives. These processes involve hydroxyl radical attack on the phenyl ring, the N,N-dimethylamine group and the central carbon atom. The Vibrio fischeri acute toxicity test showed that the solution remains toxic after MG has completely disappeared. This toxicity could be assigned, at least in part, to the formation of 4-(dimethylamine)benzophenone, which has an EC(50,30 min) of 0.061 mg l(-1), and is considered "very toxic to aquatic organisms" by current EU legislation.

Application of a multivariate analysis method for non-target screening detection of persistent transformation products during the cork boiling wastewater treatment.

Cork boiling wastewater is a very complex mixture of naturally occurring compounds leached and partially oxidized during the boiling cycles. The effluent generated is recalcitrant and could cause a significant environmental impact. Moreover, if this untreated industrial wastewater enters a municipal wastewater treatment plant it could hamper or reduce the efficiency of most activated sludge degradation processes. Despite the efforts to treat the cork boiling wastewater for reusing purposes, is still not well-known how safe these compounds (original compounds and oxidation by-products) will be. The purpose of this work was to apply an HPLC-high resolution mass spectrometry method and subsequent non-target screening using a multivariate analysis method (PCA), to explore relationships between samples (treatments) and spectral features (masses or compounds) that could indicate changes in formation, degradation or polarity, during coagulation/flocculation (C/F) and photo-Fenton (PhF). Although, most of the signal intensities were reduced after the treatment line, 16 and 4 new peaks were detected to be formed after C/F and PhF processes respectively. The use of this non-target approach showed to be an effective strategy to explore, classify and detect transformation products during the treatment of an unknown complex mixture.

Advanced oxidation process-biological system for wastewater containing a recalcitrant pollutant.

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).

Combination of nanofiltration and ozonation for the remediation of real municipal wastewater effluents: Acute and chronic toxicity assessment.

The purpose of this work was to study the ozonation of nanofiltration (NF) retentates of real municipal wastewater treatment plant (MWTP) effluents for removal of microcontaminants (MCs) and toxicity. MCs present in these effluents were monitored using LC-MS/MS. Acute and chronic toxicity was addressed with Daphnia magna, Vibrio fischeri and Selenastrum capricornutum. Up to 40 MCs were found, most of them in concentrations over 100ng/L. 90% degradation of the sum of MCs was the critical point of comparison. When the NF membrane system was applied to MWTP effluents, treatment of NF rejection needed 2.75-4.5g O3/m3,4.5g O3/m3, which is less than 50% of the ozone needed for direct treatment of MWTP effluent. Treatment time (lower than 11min) was not influenced by MCs concentration, at least in the range tested (25-190µg/L). It has been demonstrated that consumption of ozone increased with organic load and inorganic content of different real effluents. MCs were eliminated by ozonation but acute toxicity (against V. fischeri and D. magna) increased. Chronic toxicity results were different and contrary in D. magna and S. capricornutum, due to the generation of new transformation products more toxic to D. magna than the parent contaminants. S. capricornutum inhibition percentage decreased in all cases after ozonation treatment. According to these results, before ozonation is implemented in MWTPs for the removal of MCs, the transformation products must first be examined and the treatment time or ozone doses should be extended to complete degradation if necessary.

Cork boiling wastewater treatment and reuse through combination of advanced oxidation technologies.

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 FeCl3 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.