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A validation study using recycled ultrafiltration membranes (r-UF) on an aerobic membrane bioreactor (aMBR) was conducted for the first time. Four different polyethersulfone (PES) membranes were tested using synthetic urban wastewater (COD 0.4-0.5 g/L) during two experimental periods: (i) recycled ultrafiltration membrane (r-UF) and commercial UF membrane (molecular weight cut-off (MWCO) 150 kDa) (c-150 kDa); (ii) r-UF membrane modified by dip-coating using catechol (CA) and polyethyleneimine (PEI) (mr-UF) and c-20 kDa membrane. Permeability, fouling behavior, and permeate quality were evaluated. Extensive membrane characterization was conducted using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy-dispersive X-ray (EDX), and confocal laser scanning microscopy (CLSM). Permeate quality for r-UF and mr-UF membranes was excellent and comparable to that obtained using commercial membranes under similar conditions. Additionally, r-UF and mr-UF membranes presented a steadier performance time. Additionally, r-UF membrane demonstrated less tendency to be fouled (Rf, m-1) r-UF 7.92 ± 0.57 × 1012; mr-UF 9.90 ± 0.14 × 1012, c-150 kDa 1.56 ± 0.07 × 1013 and c-20 kDa 1.25 ± 0.50 × 1013. The r-UF membrane showed an excellent antibiofouling character. Therefore, r-UF membranes can be successfully implemented for wastewater treatment in aMBR, being a sustainable and cost-effective alternative to commercial membranes that can contribute to overcome membrane fouling and membrane replacement issues.

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The direct end-of-life recycling of reverse osmosis membranes (RO) into recycled nanofiltration (r-NF) membranes has been pointed out as a circular technology. For the first time, an environmental analysis of the whole life cycle of r-NF membranes was performed, focused on their usage. The carbon footprint (CF) of NF water treatment processes (Functional Unit: 1 m3 of treated water) with different pressure vessel (PV) designs and energy sources using r-NF and commercial NF-270-400 was quantified. Moreover, to compensate for the lower permeability of the r-NF, two design strategies were assessed: A) an increment in inlet pressure, and B) an increase in the number of modules. The inventory included energy modelling for each design and membrane. The interaction of both strategies with the permeability and service life of r-NF, together with different energy sources, was assessed using a novel hybrid analytical-numerical method. The relevance of energy use at the usage stage was highlighted. Therefore, r-NF permeability is the foremost relevant parameter for the definition of CF. The low impact of the r-NF replacement favoured strategy B. The use of an environmental indicator (CF) made it possible to identify the frontiers of the recyclability and applicability of r-NF membranes.

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One of the alternative sources to tackle the problem of water shortage is the use of reclaimed water from wastewater treatment plants for irrigation purposes. However, when the wastewater has a high conductivity value, it becomes unusable for crop irrigation and needs a more specific treatment. In this work, recycled nanofiltration (rNF) membranes and anion-exchange membranes (rAEMs) obtained from end-of-life RO membranes were validated to evaluate their application capability in saline wastewater treatment. The use of recycled membranes may represent an advantage due to their lower cost and reduced environmental impact associated with their production, which integrates membrane-based technology into a circular economy model. Both recycled membranes were tested in crossflow filtration and electrodialysis (ED) systems. The results of the rNF membrane showed a high selective rejection of divalent ions (SO42− (>96%) and Ca2+ and Mg2+ (>93%)). In the case of the ED process, the comparison between rAEMs and commercial membranes showed an appropriate demineralization rate without compromising the power consumption. Finally, the quality of both system effluents was suitable for irrigation, which was compared to the WHO guideline and validated by the 7-week lettuce crop study.

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This work explores the application of Reverse Osmosis (RO) upcycled membranes, as Anion Exchange Membranes (AEMs) in Donnan Dialysis (DD) and related processes, such as the Ion Exchange Membrane Bioreactor (IEMB), for the removal of nitrate from contaminated water, to meet drinking water standards. Such upcycled membranes might be manufactured at a lower price than commercial AEMs, while their utilization reinforces the commitment to a circular economy transition. In an effort to gain a better understanding of such AEMs, confocal µ-Raman spectroscopy was employed, to assess the distribution of the ion-exchange sites through the thickness of the prepared membranes, and 2D fluorescence spectroscopy, to evaluate alterations in the membranes caused by fouling and chemical cleaning The best performing membrane reached a 56% average nitrate removal within 24 h in the DD and IEMB systems, with the latter furthermore allowing for simultaneous elimination of the pollutant by biological denitrification, thus avoiding its discharge into the environment. Overall, this work validates the technical feasibility of using RO upcycled AEMs in DD and IEMB processes for nitrate removal. This membrane recycling concept might also find applications for the removal and/or recovery of other target negatively charged species.

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The use of recycled ultrafiltration (r-UF) membranes, originating from end-of-life reverse osmosis membranes, as submerged flat-sheet membranes in an aerobic membrane bioreactor (aMBR) system is described herein for the first time. A feasibility study of this new approach was performed in a laboratory-scale aMBR system. The r-UF membrane performance was evaluated in terms of permeability, fouling behavior, and permeate quality using a widely used commercial flat sheet microfiltration membrane (c-MF) as a reference. Tests were conducted under steady-flux operation (at 12 and 14 L·m-2·h-1) and a variable trans-membrane pressure. Synthetic wastewater simulating urban wastewater characteristics with approx. 0.4-0.5 g/L COD concentration was used as the feed. The obtained results showed that the rejection performance of the r-UF membrane was similar to the performance of the commercial flat sheet microfiltration membrane (c-MF) under comparable operating conditions. Moreover, concerning fouling behavior, the r-UF membrane exhibited higher fouling resistance compared with the c-MF membrane, although the permeability decline rate was lower. Both membranes had comparable fouling mechanisms behavior, with cake layer fouling resistance accounting for approx. 60% of the total fouling resistance. Finally, a preliminary economic assessment pointed out the potential competitiveness of using r-UF membranes for aMBRs (5.9-10.9 EUR·m-2) and the scaling-up challenges toward industrial applications.

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Conventional wastewater treatment technologies are costly and energy demanding; such issues are especially remarkable when small communities have to clean up their pollutants. In response to these requirements, a new variety of nature-based solution, so-called METland®, has been recently develop by using concepts from Microbial Electrochemical Technologies (MET) to outperform classical constructed wetland regarding wastewater treatment. Thus, the current study evaluates two operation modes (aerobic and aerobic-anoxic) of a full-scale METland®, including a Life Cycle Assessment (LCA) conducted under a Net Environmental Balance perspective. Moreover, a combined technical and environmental analysis using a Net Eutrophication Balance (NEuB) focus concluded that the downflow (aerobic) mode achieved the highest removal rates for both organic pollutant and nitrogen, and it was revealed as the most environmentally friendly design. Actually, aerobic configuration outperformed anaero/aero-mixed mode in a fold-range from 9 to 30%. LCA was indeed recalculated under diverse Functional Units (FU) to determine the influence of each FU in the impacts. Furthermore, in comparison with constructed wetland, METland® showed a remarkable increase in wastewater treatment capacity per surface area (0.6 m2/pe) without using external energy. Specifically, these results suggest that aerobic-anoxic configuration could be more environmentally friendly under specific situations where high N removal is required. The removal rates achieved demonstrated a robust adaptation to influent variations, revealing a removal average of 92% of Biology Oxygen Demand (BOD), 90% of Total Suspended Solids (TSS), 40% of total nitrogen (TN), and 30% of total phosphorus (TP). Moreover, regarding the global warming category, the overall impact was 75% lower compared to other conventional treatments like activated sludge. In conclusion, the LCA revealed that METland® appears as ideal solution for rural areas, considering the low energy requirements and high efficiency to remove organic pollutants, nitrogen, and phosphates from urban wastewater.

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The present work shows a methodology for the preparation of membranes with a high affinity for nitrates. For this purpose, a polymeric mixture containing an anion exchange resin was extended on a recycled pressure filtration membrane used as mechanical support. Different ion exchange resins were tested. The influence in ion fractionation of (i) the type of ion exchange resin, (ii) the use of a recycled membrane as support and (iii) the operating current density during the separation process were studied. Results revealed that the employed anion exchange resin could tune up the transport numbers of the anions in the membrane and enhance the transport of nitrates over sulfates. The use of the recycled filtration membrane as support further increased the transport of nitrates in detriment of sulfates in nitrate-selective membranes. Moreover, it considerably improved the mechanical stability of the membranes. Lowering the operational current density also boosted ion fractionation. In addition, the use of recycled membranes as support in membrane preparation is presented as an alternative management route of discarded reverse osmosis membranes, coupling with the challenging management of waste generated by the desalination industry. These membranes could be used for nitrate recovery from wastewater or for nitrate separation from groundwater.

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This data includes the geographical data, the Life Cycle Inventory data and Life Cycle Assessment data of the implementation of end-of-life (EoL) reverse osmosis (RO) direct recycling implementation at full scale in a Spanish region. Besides, the data allows the comparison of the environmental profile between recycled membrane products with the commercial counterparts. The EoL-RO stock potential was analysed constrained to the Segura´s watershed. However, the distribution of recycled membranes was considered within the European Union´s borders. The International Life Cycle Data system (ILCD) midpoint impact categories and the indicator Service Life Ratio (SLR) are presented. This data could be used for deepening analyses as the externalities monetarisation or business model identification or policymakers This data article is related to J. Senán-Salinas, A. Blanco, R. García-Pacheco, J. Landaburu-Aguirre, E- García-Calvo. J Prospective Life Cycle Assessment and economic analysis of direct recycling of end-of-life reverse osmosis membranes based on Geographic Information Systems. J. Clean. Prod. In Press.

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In this study, an activation treatment for recycled anion exchange membranes is proposed. Following the circular economy approach, these membranes were prepared by using end-of-life reverse osmosis membranes as mechanical support. The end-of-life membrane was previously used and discarded by desalination plants after overcoming its lifespan. The activation treatment was based on the subsequent immersion of the membranes in diluted acid and alkali solutions. This treatment promoted the complete dissociation of the functional groups in the membrane, making them more reactive to the counter ions. The effects of acid and alkali concentrations and exposition times on the electrochemical properties were studied and the best combination was selected. In such a way, a decrease of 37% in membrane electrical resistance was achieved. The performance of activated and non-activated membranes in brackish water desalination by electrodialysis was compared. The results showed that the proposed activation treatment increased the flux of fresh water more than four-fold (from 1.2 to 4.9 L h-1·m-2), with a considerable reduction of energy consumption (from 5.2 to 3.0 kWh·m-3) and a great improvement in current efficiency (from 38% to 71%). In conclusion, this work shows a simple and low cost methodology for the improvement of the electrochemical properties of recycled electromembranes and thus, their performance in electrodialysis.

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The continuous ozonation of the antibiotic ofloxacin (OFX) has been performed using a synthetic water matrix and in a sewage treatment plant (STP) effluent. The aim was to study the effect of the water matrix on the ozonation with particular emphasis on the aquatic toxicity of treated water. OFX was completely removed in both water matrices, although the amount of ozone consumed for its depletion was strongly matrix-dependent. The extent of mineralization was limited and a number of intermediate transformation products (TPs) appeared, twelve of which could be identified. OFX reaction pathway includes the degradation of piperazinyl and quinolone moieties. The further oxidation of TPs gave rise to the formation and accumulation of carboxylic acids, aldehydes, nitrogen-containing organic compounds and inorganic ions. Aquatic toxicity of treated mixtures was assessed using four standard species: the bacteria Vibrio fischeri and Pseudomonas putida as target organisms and the algae Pseudokirchneriella subcapitata and the protozoan Tetrahymena thermophila as non-target organisms. OFX was toxic for the bacteria and the microalgae at the spiked concentration in untreated water. However, the continuous ozonation at the upper operational limit removed its toxic effects. T. thermophila was not affected by OFX, but was sensitive to STP effluent.

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The aquatic toxicity of eight preservatives frequently used in personal care products (PCPs) (iodopropynyl butylcarbamate, bronopol, diazolidinyl urea, benzalkonium chloride, zinc pyrithione, propylparaben, triclosan and a mixture of methylchloroisothiazolinone and methylisothiazolinone) was assessed by means of two different approaches: a battery of bioassays composed of single species tests of bacteria (Vibrio fischeri and Pseudomonas putida) and protozoa (Tetrahymena thermophila), and a whole biological community resazurin-based assay using activated sludge. The tested preservatives showed considerable toxicity in the studied bioassays, but with a marked difference in potency. In fact, all biocides except propylparaben and diazolidinyl urea had EC50 values lower than 1 mg L(-1) in at least one assay. Risk quotients for zinc pyrithione, benzalkonium chloride, iodopropynyl butylcarbamate and triclosan as well as the mixture of the studied preservatives exceeded 1, indicating a potential risk for the process performance and efficiency of municipal sewage treatment plants (STPs). These four single biocides explained more than 95% of the preservative mixture risk in all bioassays. Each individual preservative was also tested in combination with an industrial wastewater (IWW) from a cosmetics manufacturing facility. The toxicity assessment was performed on binary mixtures (preservative + IWW) and carried out using the median-effect principle, which is a special case of the concept of Concentration Addition (CA). Almost 70% of all experiments resulted in EC50 values within a factor of 2 of the values predicted by the median-effect principle (CI values between 0.5 and 2). The rest of the mixtures whose toxicity was mispredicted by CA were assessed with the alternative concept of Independent Action (IA), which showed higher predictive power for the biological community assay. Therefore, the concept used to accurately predict the toxicity of mixtures of a preservative with a complex industrial wastewater depends on degree of biological complexity.

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This article reports novel results on the toxic mechanisms of action of amine- and hydroxyl-terminated poly(amidoamine) (PAMAM) dendrimers toward microorganisms of environmental relevance, namely a cyanobacterium of the genus Anabaena and the green alga Chlamydomonas reinhardtii. We used PAMAM ethylenediamine core dendrimers from generations G2 to G4, which displayed a positive charge, measured as ζ-potential, in culture media. All amine-terminated and most remarkably the G4 hydroxyl-terminated dendrimer inhibited the growth of both microorganisms. The effect on the growth of the green alga was significantly higher than that on the cyanobacterium. With concentrations expressed in terms of molarity, there was a clear relationship between dendrimer generation and toxicity, with higher toxicity for higher generation. Hormesis was observed for hydroxyl-terminated dendrimers at low concentrations. The cationic dendrimers and G4-OH significantly increased the formation of reactive oxygen species (ROS) in both organisms. ROS formation was not related with the chloroplast or photosynthetic membranes and photosystem II photochemistry was unaffected. Cell damage resulted in cytoplasm disorganization and cell deformities and was associated to an increase in ROS formation and lipid peroxidation in mitochondria in the green alga; cell wall and membrane disruption with apparent loss of cytoplasmic contents was found in the cyanobacterium. It was determined for the first time that cationic PAMAM dendrimers were quickly and largely internalized by both organisms. These results warn against the generalization of the use of dendrimers, which may pose significant risk for the environment and particularly for primary producers which are determinant for the health of natural ecosystems.

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Aggregation raises attention in Nanotoxicology due to its methodological implications. Aggregation is a physical symptom of a more general physicochemical condition of colloidal particles, namely, colloidal stability. Colloidal stability is a global indicator of the tendency of a system to reduce its net surface energy, which may be achieved by homo-aggregation or hetero-aggregation, including location at bio-interfaces. However, the role of colloidal stability as a driver of ENM bioactivity has received little consideration thus far. In the present work, which focuses on the toxicity of nanoscaled Fe° nanoparticles (nZVI) towards a model microalga, we demonstrate that colloidal stability is a fundamental driver of ENM bioactivity, comprehensively accounting for otherwise inexplicable differential biological effects. The present work throws light on basic aspects of Nanotoxicology, and reveals a key factor which may reconcile contradictory results on the influence of aggregation in bioactivity of ENMs.

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This article deals with the degradation of a third-generation (G3) poly(amidoamine) (PAMAM) dendrimer under ozonation and irradiation. The identification and quantification of G3 PAMAM dendrimer and its transformation products has been performed by liquid chromatography-electrospray ionization-hybrid quadrupole time-of-flight-mass spectrometry. The dendrimer was completely depleted by ozone in less than 1 min. The effect of ultraviolet irradiation was attributed to hydroxyl-mediated oxidation. The transformation products were attributed to the oxidation of amines, which resulted in highly oxidized structures with abundance of carboxylic acids, which started from the formation of amine oxide and the scission of the CN bond of the amide group. We studied the toxicity of treated mixtures for six different organisms: the acute toxicity for the bacterium Vibrio fischeri and the microcrustacean Daphnia magna, the multigenerational growth inhibition of the alga Pseudokirchneriella subcapitata, and the seed germination phytotoxicity of Licopersicon esculentum, Lactuca sativa and Lolium perenne. Ozonation and irradiation originated transformation products are more toxic than the parent dendrimer. The toxicity of the dendrimer for the green alga was linked to a strong increase of intracellular reactive oxygen species with intense lipid peroxidation.

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This study aims to assess the removal of a set of non-polar pollutants in biologically treated wastewater using ozonation, ultraviolet (UV 254 nm low pressure mercury lamp) and visible light (Xe-arc lamp) irradiation as well as visible light photocatalysis using Ce-doped TiO2. The compounds tracked include UV filters, synthetic musks, herbicides, insecticides, antiseptics and polyaromatic hydrocarbons. Raw wastewater and treated samples were analyzed using stir-bar sorptive extraction coupled with comprehensive two-dimensional gas chromatography (SBSE-CG × GC-TOF-MS). Ozone treatment could remove most pollutants with a global efficiency of over 95% for 209 µM ozone dosage. UV irradiation reduced the total concentration of the sixteen pollutants tested by an average of 63% with high removal of the sunscreen 2-ethylhexyl trans-4-methoxycinnamate (EHMC), the synthetic musk 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (tonalide, AHTN) and several herbicides. Visible light Ce-TiO2 photocatalysis reached ~70% overall removal with particularly high efficiency for synthetic musks. In terms of power usage efficiency expressed as nmol kJ(-1), the results showed that ozonation was by far the most efficient process, ten-fold over Xe/Ce-TiO2 visible light photocatalysis, the latter being in turn considerably more efficient than UV irradiation. In all cases the efficiency decreased along the treatments due to the lower reaction rate at lower pollutant concentration. The use of photocatalysis greatly improved the efficiency of visible light irradiation. The collector area per order decreased from 9.14 ± 5.11 m(2) m(-3) order(-1) for visible light irradiation to 0.16 ± 0.03 m(2) m(-3) order(-1) for Ce-TiO2 photocatalysis. The toxicity of treated wastewater was assessed using the green alga Pseudokirchneriella subcapitata. Ozonation reduced the toxicity of treated wastewater, while UV irradiation and visible light photocatalysis limited by 20-25% the algal growth due to the accumulation of reaction by-products. Three transformation products were identified and tracked along the treatments.

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RATIONALE: Poly(amidoamine) PAMAM dendrimers are highly water soluble and are used as flexible scaffolding or nanocontainers to conjugate, complex or encapsulate therapeutic drugs to overcome intrinsically weak characteristics such as solubilization in aqueous medium. To provide a reliable method for the quantitation of PAMAM dendrimers in aqueous medium, we report here a validation study which was developed in a complex wastewater matrix to evaluate the matrix effect in the electrospray ionization (ESI) source. METHODS: PAMAM dendrimers (generations G0 to G3) were identified and quantitated in aqueous medium using liquid chromatography interfaced to a hybrid quadrupole/time-of-flight mass analyzer. This approach used the high resolving power of isotopic clusters and mass accuracy of the instrument, with especial attention to the tandem mass spectrometric (MS/MS) capabilities. The formation of multiply charged ions of PAMAM dendrimers in the ESI source and their later fragmentation allowed fragmentation paths to be determined and structural assignments to be made. RESULTS: The analytical strategy allowed dendrimer identification with a high degree of confidence obtained by accurate mass and high resolution with mass errors below 5 ppm and 10 ppm in MS and MS/MS modes. The parameters of validation in spiked matrix were: limits of quantification in the range of 0.12 to 1.25 µM depending on the generation, linearity (R >0.996), repeatability (R.S.D. <6.7%) and reproducibility (R.S.D. <10.8%). CONCLUSIONS: Accurate mass measurement, elemental composition, and charge state assignment through the resolution of isotopic clusters of product and precursor ions, confers enhanced confidence on PAMAM dendrimer characterization. This selectivity provided high discriminating capacity of PAMAM dendrimers against matrix interferences. Because of the reliable and reproducible quantitation by LC/ESI-QTOF-MS, analysis of PAMAM dendrimers in an aqueous matrix is feasible.

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Wastewater samples from the secondary clarifier of two treatment plants were spiked in the microgram-to-tens-of-microgram per liter range with diuron (herbicide), ibuprofen and diclofenac (anti-inflammatory drugs), sulfamethoxazole and erythromycin (antibiotics), bezafibrate and gemfibrozil (lipid regulators), atenolol (ß-blocker), carbamazepine (anti-epileptic), hydrochlorothiazide (diuretic), caffeine (stimulant) and N-acetyl-4-amino-antipiryne, a metabolite of the antipyretic drug dypirone. They were subsequently ozonated in continuous flow using 1.2L lab-scale bubble columns. The concentration of all spiking compounds was monitored in the outlet stream. The effects of varying ozone input, expressed as energy per unit volume, and water flow rate, and of using single or double column were studied in relation to the efficiency of ozone usage and the ratio of pollutant depletion. The ozone dosage required to treat both wastewaters with pollutant depletion of >90% was in the 5.5-8.5 mg/L range with ozone efficiencies greater than 80% depending on the type of wastewater and the operating conditions. This represented 100-200 mol of ozone transferred per mole of pollutant removed. Direct and indirect environmental impacts of ozonation were assessed according to Life Cycle Assessment, a technique that helped identify the most effective treatments in terms of potential toxicity reduction, as well as of toxicity reduction per unit mass of greenhouse-gas emissions, which were used as an indicator of environmental efficiency. A trade-off between environmental effectiveness (toxicity reduction) and greenhouse-gas emissions was observed since maximizing toxicity removal led to higher greenhouse-gas emissions, due to the latter's relatively high ozone requirements. Also, there is an environmental trade-off between effectiveness and efficiency. Our results indicate that an efficient use of ozone was not compatible with a full pollutant removal.

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The effect of nanoceria on two aquatic photosynthetic organisms of ecological relevance, a green alga and a cyanobacterium, is reported. The main bioenergetic process of these organisms, photosynthesis, was studied by measuring both oxygen evolution and chlorophyll a fluorescence emission parameters. Nanoceria significantly inhibited photosynthesis in the cyanobacterium in the entire range of concentrations tested (0.01-100 mg/L), while a dual effect of nanoceria was found in the green alga with slight stimulation at low concentrations and strong inhibition at the highest concentrations tested. Chlorophyll a fluorescence experiments indicated that nanoceria had a significant impact on the primary photochemical processes of photosystem II. The primary cause of the observed photosynthetic inhibition by nanoceria is an excessive level of ROS formation; the results indicated a strong generation of reactive oxygen species (ROS) which caused oxidative damage, as evidenced by lipid peroxidation in both photosynthetic organisms. It is proposed that nanoceria can increase the production of hydrogen peroxide (a normal ROS by-product of light-driven photosynthesis) in both the green alga and the cyanobacterium; through an oxidative reaction, these ROS cause lipid peroxidation, compromising membrane integrity and also seriously impairing photosynthetic performance, eventually leading to cell death.

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Synthetic musks have been reported in wastewaters at concentrations as high as tens of micrograms per litre. The two most significant polycyclic musk fragrance compounds are 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran (HHCB, trade name galaxolide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (AHTN, trade name tonalide®). We report the result of several irradiation and advanced oxidation processes carried out on samples of the effluent of a wastewater treatment plant located in Alcalá de Henares, Madrid. Wastewater samples were pre-ozonated and spiked with 500 ng/L of tonalide or galaxolide in order to obtain final concentrations in the same order as the raw effluent. The treatments assayed were ozonation with and without the addition of hydrogen peroxide (O3, O3/H2O2), ultraviolet (254 nm low pressure mercury lamp) and xenon-arc visible light irradiation alone and in combination with ozone (UV, O3/UV, Xe, O3/Xe) and visible light photocatalytic oxidation using a Ce-doped titanium dioxide photocatalyst performed under continuous oxygen or ozone gas bubbling (O2/Xe/Ce-TiO2, O3/Xe/Ce-TiO2). In all cases, samples taken at different contact times up to 15 min were analyzed. An analytical method based on stir bar sorptive extraction (SBSE), followed by comprehensive two-dimensional gas chromatography (SBSE-GC × GC-TOF-MS), was used for the automatic searching and evaluation of the synthetic musks and other nonpolar or semipolar contaminants in the wastewater samples. In all cases tonalide was more easily removed than galaxolide. The best results for the latter (more than 75% removal after 5 min on stream) were obtained from ozonation (O3) and visible light photocatalytic ozonation (O3/Xe/Ce-TiO2). A significant removal of both pollutants (∼60% after 15 min) was also obtained during visible light photocatalysis (O2/Xe/Ce-TiO2). UV radiation was able to deplete tonalide (+90%) after 15 min but only reduced the concentration of galaxolide to about half of its initial concentration. The toxicity of treated samples decreased for O3/UV and O3/Ce-TiO2, but increased during irradiation processes UV, Xe and Xe/Ce-TiO2. Ozone treatments tend to decrease toxicity up to a certain dosage, from which point the presence of toxic transformation products has adverse effects on aquatic microorganisms.

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This study aims to assess the occurrence, fate and temporal and spatial distribution of anthropogenic contaminants in a river subjected to different pressures (industrial, agricultural, wastewater discharges). For this purpose, the Henares River basin (central Spain) can be considered a representative basin within a continental Mediterranean climate. As the studied river runs through several residential, industrial and agricultural areas, it would be expected that the chemical water quality is modified along its course. Thereby the selection of sampling points and timing of sample collection are critical factors in the monitoring of a river basin. In this study, six different monitoring campaigns were performed in 2010 and contaminants were measured at the effluent point of the main wastewater treatment plant (WWTP) in the river basin and at five different points upstream and downstream from the WWTP emission point. The target compounds evaluated were personal care products (PCPs), polycyclic aromatic hydrocarbons (PAHs) and pesticides. Results show that the river is clearly influenced by wastewater discharges and also by its proximity to agricultural areas. The contaminants detected at higher concentrations were the PCPs. The spatial distribution of the contaminants indicates that the studied contaminants persist along the river. In the time period studied no great seasonal variations of PCPs at the river collection points were observed. In contrast, a temporal trend of pesticides and PAHs was observed. Besides the target compounds, other new contaminants were identified and evaluated in the water samples, some of them being investigated for the first time in the aquatic environment. The behaviour of three important transformation products was also evaluated: 9,10-anthracenodione, galaxolide-lactone and 4-amino-musk xylene. These were found at higher concentrations than their parent compounds, indicating the significance of including the study of transformation products in the monitoring programmes.

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