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Fullerenes are carbon nanomaterials that have awaken a strong interest due to their adsorption properties and potential applications in many fields. However, there are some gaps of information about their effects and bioconcentration potential in the aquatic biota. In the present work, freshwater biofilms and snails (Radix sp.) were exposed to fullerene C60 aggregates, at concentrations in the low μg/L order, in mesocosms specifically designed to mimic the conditions of a natural stream. The bioconcentration factors of C60 fullerene and its main transformation product, [6,6]C60O epoxide, were studied to the mentioned organisms employing analyses by liquid chromatography coupled to high-resolution mass spectrometry. Our results show that C60 fullerene and its [6,6]C60O present a low bioconcentration factor (BCF) to biofilms: BCFC60 = 1.34 ± 0.95 L/kgdw and BCFC60O = 1.43 ± 0.72 L/kgdw. This suggests that the sorption of these aggregates to biota may be less favoured than it would be suggested by its hydrophobic character. According to our model, the surface of fullerene aggregates is saturated with [6,6]C60O molecules, which exposes the polar epoxide moieties in the surface of the aggregates and decreases their affinity to biofilms. In contrast, freshwater snails showed a moderate capacity to actively retain C60 fullerenes in their organism (BAFC60 = 2670 ± 3070 L/kgdw; BAFC60O = 1330 ± 1680 L/kgdw), probably through ingestion. Our results indicate that the bioaccumulation of these carbon nanomaterials can be hardly estimated using their respective octanol-water partition coefficients, and that their colloidal properties, as well as the feeding strategies of the tested organism, play fundamental roles. © 2019 Elsevier Inc., This work was supported by the Spanish Ministry of Economy and Competitiveness through the project NANO-transfer (ERA-NET SIINN PCIN-2015-182-CO2-01) and by the Generalitat de Catalunya (Consolidated Research Groups “2014 SGR 418 – Water and Soil Quality Unit” and “2014 SGR 291 – ICRA”). Lúcia H.M.L.M. Santos acknowledges the Juan de la Cierva program (IJCI-2017-32747) and Julio C. López-Doval thanks the program Juan de la Cierva from the Spanish Ministry of Economy and Competitiveness (IJCI-2015-23644). Appendix A

Bioaccumulation of pharmaceuticals in fish exposed to contaminated water can be shaped by their capability to metabolize these xenobiotics, affecting their toxicity and animal welfare. In this study the in vivo metabolization of the antidepressant venlafaxine by the juvenile marine fish meagre (Argyrosomus regius) was evaluated using a combined target and suspect screening analytical approach. Thirteen venlafaxine metabolites were identified, namely N-desmethylvenlafaxine and N,N-didesmethylvenlafaxine, which were unequivocally identified using analytical standards, and 11 more tentatively identified by suspect screening analysis, including two Phase II metabolites formed by amino acid conjugation. All of them were detected in the liver, while in plasma and brain only 9 and 6 metabolites, respectively, were detected. Based on these findings, for the first time, a tentative metabolization pathway of venlafaxine by A. regius is proposed. Contrarily to what happen in humans, N-demethylation was identified as the main route of metabolization of venlafaxine by fish. Our findings highlight species-specificity in the metabolization of venlafaxine and allow a better understanding of venlafaxine's toxicokinetic in fish. These results emphasize the need to investigate the biotransformation of xenobiotics by non-target organisms to have an integrated overview of their environmental exposure and to improve future evaluations of environmental risk assessment., This work was funded by the 7th EU-FP (ECsafeSEAFOOD project; GA n° 311820) and the European Regional Development Fund (FEDER) and by Spanish Ministry of Economy and Competitiveness (PGE-2010). This work was also funded by the Spanish State Research Agency of the Spanish Ministry of Science, Innovation and Universities and European Fund for Regional Development (project PLAS-MED; FEDER-MCIU-AEI/CTM2017-89701-C3-2-R). Authors thank Generalitat de Catalunya through Consolidated Research Group (ICRA-ENV 2017 SGR 1124 & 2017 SGR 1404). ICRA researchers thank funding from CERCA program. Lúcia H.M.L.M. Santos thanks the Juan de la Cierva program (IJCI-2017-32747) and Sara Rodríguez-Mozaz thanks the Ramon y Cajal program (RYC-2014-16707) from the Spanish State Research Agency of the Spanish Ministry of Science, Innovation and Universities (AEI-MCIU). A. Jaén-Gil thanks the predoctoral grant from the Agency for Management of University and Research Grants (AGAUR) (2019FI_B2_00202) co-financed by the European Social Fund. A. Marques (IF program) and A.L. Maulvault (Project FishBudget PTDC/BIA-BMA/28630/2017) thank the Portuguese Foundation for Science and Technology.

The so-called marine litter, and in particular microplastics (MPs) and nanoplastics (NPs), are ubiquitously distributed and recognised as an emerging risk for the environment and human health. It is known that marine environments are one of the most impacted areas and among them; coastal zones are the most contaminated ones. They are subjected to population pressure, tourism, harbours, desalination plants, marine traffic and fish farms. This review is focused on the Mediterranean Sea, currently considered one hot spot of microplastics pollution in the world, as a consequence of the high number of plastic marine litter generating activities and its characteristic morphology of semi-enclosed sea. MPs and NPs have been detected not only in surface water and water columns but also in sediments, deep seafloor, and biota including fish and seafood for human consumption. Because of this, different European legislation initiatives have been launched during the last years in order to prevent MPs and NPs contamination and to face derived problems. Finally, this review summarises the main problems and shortcomings associated to MPs and NPs analyses such as their identification and quantification or the necessity of standardised protocols., This work was supported by the project PLAS-MED (CTM2017-89701-C3) from the Spanish Ministry of Science, Innovation and Universities and the European Union (European Regional Development Fund, ERDF). Authors thank Generalitat de Catalunya through Consolidated Research Group (ICRA-ENV 2017 SGR 1124). Lúcia H.M.L.M. Santos thanks the Juan de la Cierva program (IJCI-2017-32747) and Sara Rodríguez-Mozaz thanks the Ramon y Cajal program (RYC-2014-16707).

The present study evaluates the removal capacity of two high rate algae ponds (HRAPs) to eliminate 12 pharmaceuticals (PhACs) and 26 of their corresponding main metabolites and transformation products. The efficiency of these ponds, operating with and without primary treatment, was compared in order to study their capacity under the best performance conditions (highest solar irradiance). Concentrations of all the target compounds were determined in both water and biomass samples. Removal rates ranged from moderate (40–60 %) to high (>60 %) for most of them, with the exception of the psychiatric drugs carbamazepine, the β-blocking agent metoprolol and its metabolite, metoprolol acid. O-desmethylvenlafaxine, despite its very low biodegradability in conventional wastewater treatment plants, was removed to certain extent (13–39 %). Biomass concentrations suggested that bioadsorption/bioaccumulation to microalgae biomass was decisive regarding the elimination of non-biodegradable compounds such as venlafaxine and its main metabolites. HRAP treatment with and without primary treatment did not yield significant differences in terms of PhACs removal efficiency. The implementation of HRAPs as secondary treatment is a feasible alternative to CAS in terms of overall wastewater treatment, including organic micropollutants, with generally higher removal performances and implying a green, low-cost and more sustainable technology., This research was funded by the Spanish Ministry of Economy and Competitiveness (FOTOBIOGAS Project CTQ2014-57293-C3-3-R) and the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No 676070 (SuPER-W). This communication reflects only the author’s view and the Research Executive Agency of the EU is not responsible for any use that may be made of the information it contains. M.J. García-Galán and L.H.M.L.M. Santos acknowledges their Juan de la Cierva research grants (FJCI-2014-22767 and IJCI-2017-34601, and IJCI-2017-32747, respectively), and M. Garfí and S. Rodríguez-Mozaz thanks the Ramon y Cajal program (RYC-2016-20059 and RYC-2014-16707, respectively), all from the Spanish Ministry of Economy and Competitiveness.

Emerging pollutants occur in complex mixtures in rivers and have the potential to interact with freshwater organisms. The chronic effects of nominal exposure to 3 μg/L of fullerenes (C60) and 1 μg/L of triclosan (TCS) alone and in a binary mixture, were evaluated using the freshwater snail Radix balthica. Pollutants accumulation, reproductive output and feeding behavior were selected as sublethal endpoints. After 21 days of exposure, we did not observe interactive effects between TCS and C60 on the studied endpoints, except for the accumulation of C60 in R. balthica in TCS + C60 treatment, which was lower than when the fullerenes were alone. Neither TCS nor C60 caused significant effects on reproduction, expressed as number of eggs per individual, but an increase in the clutch size was observed in treatments with TCS at the third week of exposure, independently of the presence of C60 (16.15 ± 1.67 and 18.9 ± 4.01 eggs/egg mass in TCS and TCS + C60 treatments, respectively, vs. 13.17 ± 4.01 in control). The presence of C60 significantly enhanced the grazing activity of R. balthica during the first seven days (4.95 ± 1.35 and 3.91 ± 0.59% of the area grazed per individual in C60 and TCS + C60 treatments, respectively, vs 2.6 ± 0.39% in control). The accumulation of TCS was quite similar in treatments where this pollutant was present (BAF ≈ 1007 L/kg d.w.); however, the accumulation of C60 was higher when the nanoparticles were alone (BAF = 254.88 L/kg d.w.) than when it was in the binary mixture (BAF = 7.79 L/kg d.w). Overall, although TCS has been listed as an endocrine disrupter compound, no significant effects on reproduction were observed in the assayed conditions. Regarding C60, the limited effects on feeding activity and the low BAF obtained in this experiment indicate that fullerenes do not have ecological consequences of relevance at the studied environmental concentrations in freshwater snails. © 2019 Elsevier Inc., This work was supported by the Spanish Ministry of Economy and Competitiveness through the project NANO-transfer (ERA-NET SIINN PCIN-2015-182-CO2-01) and by the Generalitat de Catalunya (Consolidated Research Groups “2014 SGR 418 – Water and Soil Quality Unit” and “2014 SGR 291 – ICRA”). Julio C. López-Doval (IJCI-2015-23644), Lúcia H.M.L.M. Santos (FJCI-2014-22377 and IJCI-2017-32747) and Anna Freixa (FJCI-2017-33171) acknowledge the Juan de la Cierva program from the Spanish Ministry of Economy and Competitiveness. Sara Rodriguez-Mozaz acknowledges the Ramon y Cajal program (RYC-2014-16707).

This work aims to assess, individually and in mixtures, possible phytotoxic effects of three pharmaceuticals (paracetamol, ibuprofen and amoxicillin) on germination and early growth of Lactuca sativa seeds. Pharmaceuticals are an important group of emerging contaminants, whose presence has been described in several environmental compartments, including soils. However, knowledge on their possible impact in terrestrial organisms is still sparse and even more when mixtures are considered. Germination tests are important to evaluate the quality of soil and the toxic effects that contaminants can pose to plants. The acute effects of individual pharmaceuticals as well as binary and ternary mixtures were assessed using different endpoints, namely: percentage of seed germination, root elongation, shoot and leaf length, after an exposure time of five days. Overall, in the exposure of L. sativa seeds to individual pharmaceuticals there are indications of acute toxicity in the early plant growth. However, this inhibitory effect tends to be cancelled in the acute exposure to mixtures. This study shows the importance of evaluating the toxicity of mixtures of pharmaceuticals, since they might have distinct toxic effects when compared to the single compounds, and also because, probably, it is the closest scenario to the reality that can be found in the environment., This work received financial support from the European Regional Development Fund (ERDF) through COMPETE – Operational Competitiveness Programme and national funds provided by FCT – Foundation for Science and Technology under the projects UID/QUI/50006/2013.

A huge variety of organic microcontaminants are presently detected in freshwater ecosystems, but there is still a lack of knowledge about their interactions, either with living organisms or with other contaminants. Actually, carbon nanomaterials like fullerenes (C60) can act as carriers of organic microcontaminants, but their relevance in processes like bioaccumulation and biotransformation of organic microcontaminants by organisms is unknown. In this study, mesocosm experiments were used to assess the bioaccumulation and biotransformation of three organic microcontaminants (venlafaxine, diuron and triclosan) in river biofilms, and to understand how much the concomitant presence of C60 at environmental relevant concentrations could impact these processes. Results indicated that venlafaxine exhibited the highest bioaccumulation (13% of the initial concentration of venlafaxine in water), while biotransformation was more evident for triclosan (5% of the initial concentration of triclosan in water). Furthermore, biotransformation products such as methyl-triclosan were also present in the biofilm, with levels up to 42% of the concentration of accumulated triclosan. The presence of C60 did not involve relevant changes in the bioaccumulation and biotransformation of microcontaminants in biofilms, which showed similar patterns. Nevertheless, the study shows that a detailed evaluation of the partition of the organic microcontaminants and their transformation products in freshwater systems are important to better understand the impact of the co-existence of others microcontaminants, like carbon nanomaterials, in their possible routes of bioaccumulation and biotransformation. © 2018 Elsevier Inc., This work has been funded by the Spanish Ministry of Economy and Competitiveness (project NANOTRANSFER; ERA SIINN PCIN-2015-182-C02-02 and project PLAS-MED; CTM2017-89701-C3-2-R). Authors also acknowledge the support from the Economy and Knowledge Department of the Catalan Government through Consolidated Research Group (ICRA-ENV 2017 SGR 1124 & 2017 SGR 1404). Lúcia H.M.L.M. Santos acknowledges the Juan de la Cierva Program (FJCI-2014-22377) and Sara Rodríguez-Mozaz acknowledges the Ramon y Cajal Program (RYC-2014-16707). Funding sources This work has been funded by the Spanish Ministry of Economy and Competitiveness (project NANOTRANSFER; ERA SIINN PCIN-2015-182-C02-02 and project PLAS-MED; CTM2017-89701-C3-2-R). Authors also acknowledge the support from the Economy and Knowledge Department of the Catalan Government through Consolidated Research Group (ICRA-ENV 2017 SGR 1124 & 2017 SGR 1404). Lúcia H.M.L.M. Santos acknowledges the Juan de la Cierva program (FJCI-2014-22377) and Sara Rodríguez-Mozaz acknowledges the Ramon y Cajal program (RYC-2014-16707).

The presence of antidepressants, such as venlafaxine (VFX), in marine ecosystems is increasing, thus, potentially posing ecological and human health risks. The inherent mechanisms of VFX uptake and elimination still require further understanding, particularly accounting for the impact of climate change-related stressors, such as warming and acidification. Hence, the present work aimed to investigate, for the first time, the effects of increased seawater temperature (ΔT°C = +5 °C) and pCO2 levels (ΔpCO2 ∼1000 μatm, equivalent to ΔpH = −0.4 units) on the uptake and elimination of VFX in biological tissues (muscle, liver, brain) and plasma of juvenile meagre (Argyrosomus regius) exposed to VFX through two different exposure pathways (via water, i.e. [VFX ] ∼20 μg L−1, and via feed, i.e. [VFX] ∼160 μg kg−1 dry weight, dw). Overall, results showed that VFX can be uptaken by fish through both water and diet. Fish liver exhibited the highest VFX concentration (126.7 ± 86.5 μg kg−1 and 6786.4 ± 1176.7 μg kg−1 via feed and water exposures, respectively), as well as the highest tissue:plasma concentration ratio, followed in this order by brain and muscle, regardless of exposure route. Both warming and acidification decreased VFX uptake in liver, although VFX uptake in brain was favoured under warming conditions. Conversely, VFX elimination in liver was impaired by both stressors, particularly when acting simultaneously. The distinct patterns of VFX uptake and elimination observed in the different scenarios calls for a better understanding of the effects of exposure route and abiotic conditions on emerging contaminants’ toxicokinetics.

Antidepressants, such as venlafaxine (VFX), which are considered emerging environmental pollutants, are increasingly more present in the marine environment, and recent evidence suggest that they might have adverse effects on fish behaviour. Furthermore, altered environmental conditions associated to climate change (e.g. warming and acidification) can also have a determinant role on fish behaviour, fitness and survival. Yet, the underlying interactions between these environmental stressors (pharmaceuticals exposure and climate change) are still far from being fully understood. The aim of this study was to assess behavioural responses (in juvenile meagre (Argyrosomus regius) exposed to VFX via water ([VFX] ~20 μg L−1) and via dietary sources ([VFX] ~160 μg kg−1 dry weight), as well as to increased temperature (ΔT°C = +5 °C) and high CO2 levels (ΔpCO2 ~1000 μatm; equivalent to ΔpH = −0.4 units). Overall, VFX bioaccumulation in fish plasma was enhanced under the combination of warming and acidification. VFX triggered fish exploration, whereas fish activity and shoal cohesion were reduced. Acidification alone decreased fish exploration and shoal cohesion, and reversed fish preference to turn leftwards compared to control conditions. Such alterations were further enhanced by VFX exposure. The combination of warming and acidification also reduced shoal cohesion and loss of lateralization, regardless of VFX exposure. The distinct behaviour observed when VFX contamination, acidification and warming acted alone or in combination highlighted the need to consider the likely interactive effects of seawater warming and acidification in future research regarding the toxicological aspects of chemical contaminants.

Organic micro-contaminants (OMCs) enter in freshwaters and interact with other contaminants such as carbon nanoparticles, becoming a problem of unknown consequences for river ecosystems. Carbon nanoparticles (as fullerenes C60) are good adsorbents of organic contaminants and their interaction can potentially affect their toxicity to river biofilms. We tested the C60 interactions with selected OMCs and their effects on river biofilms in different short-term experiments. In these, river biofilms were exposed to C60 and three OMCs (triclosan, diuron, or venlafaxine) and their respective mixtures with fullerenes (C60 + each OMC). The effects were evaluated on structural, molecular, and functional descriptors of river biofilms. Our results showed that C60 did not cause toxic effects in river biofilms, whereas diuron and triclosan significantly affected the heterotrophic and phototrophic components of biofilms and venlafaxine affected only the phototrophic component. The joint exposure of C60 with venlafaxine was not producing differences with respect to the former response of the toxicant, but the overall response was antagonistic (i.e., decreased toxicity) with diuron, and synergistic (i.e., increased toxicity) with triclosan. We suggest that differences in the toxic responses could be related to the respective molecular structure of each OMC, to the concentration proportion between OMC and C60, and to the possible competition between C60 pollutants on blocking the receptors of the biological cell membranes. We conclude that the presence of C60 at low concentrations modified the toxicity of OMC to river biofilms. These interactions should therefore be considered when predicting toxicity of OMC in river ecosystems. © 2018 Freixa, Acuña, Gutierrez, Sanchís, Santos, Rodriguez-Mozaz, Farré, Barceló and Sabater., We would like to thank Ferran Romero for his help in the molecular analysis, Lorenzo Proia for his help in using MicroResp technique, and Maria Casellas for laboratory assistance.

During the past 20 years, the presence of pharmaceutical active compounds (PhACs) in the water bodies has been gaining increasing attention and nowadays there is a broad acknowledgment on their consideration as an emerging environmental problem. As a response to this threat, regulatory agencies and the European Commission have implemented a regulatory framework for environmental risk assessment (ERA) of PhACs. One of the main sources of pharmaceuticals in the environment is connected to the hospital discharge into the urban system including the antibiotic resistances and large number of pathogens. Despite wastewater is normally collected and delivered to wastewater treatment plants, it has been demonstrated that the regular treatments applied in such facilities are not completely effective through a variety of pharmaceuticals that are subsequently introduced into the environment. In this document, the authors explore the occurrence in hospital wastewater and the environmental risks of three relevant pharmaceutical groups: cytostatics, antibiotics, and contrast agents.

Concurrent exposure of estuarine organisms to man-made and natural stressors has become a common occurrence. Numerous interactions of multiple stressors causing synergistic or antagonistic effects have been described. However, limited information is available on combined effects of emerging pharmaceuticals and natural stressors. This study investigated the joint effects of the antidepressant sertraline and salinity on Carcinus maenas. To improve knowledge about interactive effects and potential vulnerability, experiments were performed with organisms from two estuaries with differing histories of exposure to environmental contamination. Biomarkers related to mode of action of sertraline were employed to assess effects of environmentally realistic concentrations of sertraline at two salinity levels. Synergism and antagonism were identified for biomarkers of cholinergic neurotransmission, energy production, anti-oxidant defences and oxidative damage. Different interactions were found for the two study sites highlighting the need to account for differences in tolerance of local ecological receptors in risk evaluations.

An analytical method based on a modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure followed by ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) was developed for the analysis of psychiatric drugs in sediments. An optimized approach was applied in sample preparation by using basic acetonitrile as extraction solvent. Extraction was followed by a clean-up using dispersive solid phase extraction (dSPE) to remove matrix interfering compounds. The analytical method was validated in terms of sensitivity, linearity, recovery, intra- and inter-day precisions and method detection and quantification limits. Under optimized conditions, limits of detection ranged from 0.01 ng g−1 to 2.08 ng g−1; and recoveries between 47 and 110% with relative standard deviation (RSD) below 5%. The developed methodology was applied to sediments of two Portuguese rivers (Douro and Lima rivers) and nine out of eleven psychiatric drugs were detected in sediments at concentrations up to 26.4 ng g−1 (dry weight). To the best of our knowledge, it was the first time that the human metabolites norfluoxetine and norsertraline were detected in river sediments at levels of few nanograms per gram.