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Microplastics (MPLs) are contaminants of emerging concern (CECs) ubiquitous in aquatic environments, which can be bioaccumulated along the food chain. In this study, the accumulation of polyethylene (PE), polystyrene (PS) and polyethylene terephthalate (PET) microplastics (MPLs) of sizes below 63 μm was assessed in Mediterranean mussels (Mytilus galloprovincialis spp). Moreover, the potential of mussels to uptake and bioaccumulate other organic contaminants, such as triclosan (TCS) and per- and polyfluoroalkyl substances (PFASs), was evaluated with and without the presence of MPLs. Then, the modulation of MPLs in the human bioaccessibility of co-contaminants was assessed by in vitro assays that simulated the human digestion process. Exposure experiments were carried out in 15 L marine microcosms. The bioaccumulation and bioaccessibility of PE, PS, PET, and co-contaminants were assessed by means of liquid chromatography -size exclusion chromatography-coupled to high-resolution mass spectrometry (LC(SEC)-HRMS). Our outcomes confirm that MPL bioaccumulation in filter-feeding organisms is a function of MPL chemical composition and particle sizes. Finally, despite the lower accumulation and bioaccumulation of PFASs in the presence of MPLs, the bioaccessibility assays revealed that PFASs bioaccessibility was favoured in the presence of MPLs. Since part of the bioaccumulated PFASs are adsorbed onto MPL surfaces by hydrophobic and electrostatic interactions, these interactions easily change with the pH during digestion, and the PFASs bioaccessibility increases., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The interaction of multiple stressors in freshwater ecosystems may lead to adverse effects on aquatic communities and their ecological functions. Microplastics (MPs) are a class of contaminants of emerging concern that can exert both direct and indirect ecotoxicological effects. A growing number of studies have investigated MPs-attached microbial communities, but the interaction between MPs and substrate-associated biofilm (i.e., on natural river substrates, such as stones and sediments) remains poorly studied. In this work, the combined effects of polyethylene MPs (PE-MPs) with a particle size of 10-45 μm (2 mg/L) and the antimicrobial triclosan (TCS) (20 μg/L) were investigated on river biofilms through a short-term exposure experiment (72 h). To the best of authors' knowledge, this is the first time that the combined effects of MPs and chemical contaminants in substrate-associated river biofilms were assessed. Different response parameters were evaluated, including (i) exposure assessment and ii) contaminants effects at different levels: bacterial community composition, antibiotic resistance, extracellular polymeric substances (EPS), photosynthetic efficiency (Y eff ), and leucine aminopeptidase activity (LAPA). Triclosan was accumulated in river biofilms (1189-1513 ng/g dw) alongside its biotransformation product methyl-triclosan (20-29 ng/g dw). Also, PE-MPs were detected on biofilms (168-292 MP/cm 2 ), but they had no significant influence on the bioaccumulation and biotransformation of TCS. A moderate shift in bacterial community composition was driven by TCS, regardless of PE-MPs co-exposure (e.g., increased relative abundance of Sphingomonadaceae family). Additionally, Y eff and EPS content were significantly disrupted in TCS-exposed biofilms. Therefore, the most remarkable effects on river biofilms were related to the antimicrobial TCS, whereas single PE-MPs exposure did not alter any of the evaluated parameters. These results demonstrate that biofilms might act as environmental sink of MPs. Although no interaction between PE-MPs and TCS was observed, the possible indirect impact of other MPs-adsorbed contaminants on biofilms should be further assessed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The increasing consumption of pharmaceuticals, alongside their limited removal in wastewater treatment plants (WWTPs), have led to their ubiquitous occurrence in receiving aquatic environments. This study addresses the occurrence of 68 pharmaceuticals (PhACs) in the Ebro River Delta region (NE Spain), as well as their distribution in different environmental compartments, including surface water, sediments, biota (river biofilm and fish tissues), and field-collected plastic litter. In addition, their concentrations in serving WWTPs, as possible sources of environmental contamination, were also determined. Our study confirmed the widespread occurrence of PhACs in riverine and, to a more limited extent, coastal environments. Most frequently detected PhACs belonged to analgesics/anti-inflammatories (e.g., ibuprofen) and psychiatric drugs (e.g., venlafaxine) therapeutic groups, followed by antihypertensives (e.g., valsartan) and antibiotics (e.g., azithromycin). Seasonal differences in cumulative levels of PhACs were reported for water and sediments (winter>summer). Despite spatial gradients were not clear along the river, a non-negligible contribution of upstream Ebro sites (reference area) was highlighted, which was unexpected based on the low anthropogenic pressure. Sediments represented a minor attenuation pathway for the selected PhACs, whereas they were more heavily accumulated in biota: fish liver (up to 166 ng/g dw), river biofilms (up to 108 ng/g dw), fish plasma (up to 63 ng/mL), and fish muscle (up to 31 ng/g dw). These findings highlight the importance of biomonitoring in the characterization of polluted areas and prioritization of hazardous substances (e.g., psychiatric drugs) in aquatic systems, and a particular interest of fish plasma as non-destructive biomonitoring matrix. PhACs were also detected on plastic litter, demonstrating their role as environmental sinks for certain PhACs (e.g., analgesics/anti-inflammatories, psychiatric drugs). Overall, the widespread detection of PhACs in a variety of biotic and abiotic matrices from the lower Ebro River and Delta warns about their possible environmental implications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Contaminants of emerging concern (CEC) are still under research given the vast diversity of compounds reaching freshwater ecosystems and adverse effects they might cause. In this study, the environmental fate of 73 CEC, comprising sweeteners, stimulants and several pharmaceutical therapeutic classes, and changes in fluvial biofilm photosynthetic parameters were evaluated in a semi-arid urban river receiving diffuse and point sources of pollution (Suquía river, Argentina). Out of the 37 CEC detected, 30 were quantified in surface water (n.d. - 9826 ng/L), 10 in biofilm (n.d. - 204 ng/g d.w. ) and 9 in the clay fraction of sediments (n.d. - 64 ng/g d.w. ). CEC distribute differently among the 3 matrices: water phase presents the biggest diversity of compounds (14 CEC families), being analgesic/anti-inflammatories the most abundant family. Antibiotics largely predominated in biofilms (7 CEC families), while the stimulant caffeine and some antibiotics where the most abundant in sediments (6 CEC families). Different CEC accumulated in biofilms and sediments upstream and downstream the city, and big shifts of biofilm community occurred downstream WWTP. The shift of biofilm community upstream (F 0  > 0) and downstream the WWTP (F 0  = 0) shows a sensitive response of F 0 to the impact of WWTP. Biofilm photosynthetic parameters responded in less impacted urban sites (sites 1, 2 and 3), where significant correlations were found between ketoprofen and some antibiotics and biofilm parameters. The diversity and amount of CEC found in the urban section of Suquía river alert to the magnitude of point and non-point sources of pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The presence of pharmaceutically active compounds (PhACs) in surface water is well known, whereas their natural occurrence in biota is much less explored. The aim of this work was to evaluate the bioaccumulation of PhACs in adult toads of the neotropical species Rhinella arenarum. Three sites were selected in Buenos Aires (Argentina): a reference site (Site 1), a site with direct discharge from a secondary wastewater treatment plant (WWTP) (Site 2) and a site 300 m downstream of the WWTP discharge (Site 3). Surface water samples, as well as muscle, liver and fat bodies of toads were collected, extracted and analyzed by LC-MS/MS. Highly significant differences in total PhACs concentration in surface water (p < 0.005) were detected between Site 2 and the other sites. These concentrations ranged from 0.37 to 52.46 ng/L at Site 1, 0.71-6950.37 ng/L at Site 2, and 0.12-75.45 ng/L at Site 3. In general, bioaccumulation of PhACs in toad tissues was similar between sites and tissues of each site. The highest concentrations were detected in the muscle of toads from Site 3 (1.06-87.24 ng/g dw), followed by liver (1.77-38.10 ng/g dw) and fat bodies (0.68-20.59 ng/g dw) from Site 1. Ibuprofen (6950 ng/L), acetaminophen (3277 ng/L) and valsartan (2504 ng/L) were the compounds with the highest concentrations in surface water from Site 2, whereas acetaminophen (87.2 ng/g dw, muscle from Site 3), desloratadine (38.1 ng/g dw, liver from Site 1), and phenazone (25.9 ng/g dw, liver from Site 1) were the ones that showed the highest concentrations in biota. This is the first time a field study has examined the environmental bioaccumulation of PhACs in anurans, demonstrating their potential for monitoring the status of natural ecosystems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Pharmaceuticals and microplastics constitute potential hazards in aquatic systems, but their combined effects and underlying toxicity mechanisms remain largely unknown. In this study, a simultaneous characterization of bioaccumulation, associated metabolomic alterations and potential recovery mechanisms was performed. Specifically, a bioassay on Mediterranean mussels (Mytilus galloprovincialis) was carried out with polyethylene microplastics (PE-MPLs, 1 mg/L) and citalopram or bezafibrate (500 ng/L). Single and co-exposure scenarios lasted 21 days, followed by a 7-day depuration period to assess their potential recovery. PE-MPLs delayed the bioaccumulation of citalopram (lower mean at 10 d: 447 compared to 770 ng/g dw under single exposure), although reaching similar tissue concentrations after 21 d. A more limited accumulation of bezafibrate was observed overall, regardless of PE-MPLs co-exposure (

Coastal ecosystems are particularly vulnerable to terrestrial inputs from human-impacted areas. The prevalence of wastewater treatment plants, unable to remove contaminants such as pharmaceuticals (PhACs), leads to their continuous input into the marine environment. In this paper, the seasonal occurrence of PhACs in a semi-confined coastal lagoon (the Mar Menor, south-eastern Spain) was studied during 2018 and 2019 by evaluating their presence in seawater and sediments, and their bioaccumulation in aquatic organisms. Temporal variation in the contamination levels was evaluated by comparison to a previous study carried out between 2010 and 2011 before the cessation of permanent discharges of treated wastewater into the lagoon. The impact of a flash flood event (September 2019) on PhACs pollution was also assessed. A total of seven compounds (out of 69 PhACs analysed) were found in seawater during 2018-2019, with a limited detection frequency (<33%) and concentrations (up to 11 ng/L of clarithromycin). Only carbamazepine was found in sediments (ND-1.2 ng/g dw), suggesting an improved environmental quality in comparison to 2010-2011 (when 24 and 13 compounds were detected in seawater and sediments, respectively). However, the biomonitoring of fish and molluscs showed a still remarkable accumulation of analgesic/anti-inflammatory drugs, lipid regulators, psychiatric drugs and β-blocking agents, albeit not higher than in 2010. The flash flood event from 2019 increased the prevalence of PhACs in the lagoon, compared to the 2018-2019 sampling campaigns, especially in the upper water layer. After the flash flood the antibiotics clarithromycin and sulfapyridine yielded the highest concentrations ever reported in the lagoon (297 and 145 ng/L, respectively), alongside azithromycin in 2011 (155 ng/L). Flash flood events associated with sewer overflows and soil mobilisation, which are expected to increase under climate change scenarios, should be considered when assessing the risks posed by pharmaceuticals to vulnerable aquatic ecosystems in the coastal areas., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

This work describes the development of analytical workflows based on pyrolysis coupled with gas chromatography-mass spectrometry (Pyr-GC/MS) for the qualitative and quantitative analysis of 12 of the most common plastic polymers in environmental samples. The most suitable characteristic pyrolyzate compounds and respective indicator ions were selected for each polymer in order to obtain the most appropriate response for analytical purposes. Additionally, commercial pyrolyzates and polymers libraries were used to confirm the identity of the detected microplastics. The method was validated, showing a good linearity for all the plastic polymers (R 2 > 0.97) and limits of detection between 0.1 (polyurethane) to 9.1 µg (polyethylene). The developed methodology was successfully applied for the analysis of plastic polymers in environmental microplastic samples collected in three Mediterranean beaches (NE Spain).•Fast and reproducible Pyr-GC/MS method for the analysis of the 12 most common plastic polymers in a single GC/MS run•Straightforward analytical workflows using pyrolyzates and polymers libraries enable a fast identification and quantification of microplastics in environmental samples., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors. Published by Elsevier B.V.)

In this study, a non-target metabolomic approach was used to investigate changes in the metabolome of juvenile meagre (Argyrosomus regius) exposed to venlafaxine (20 µg/L). A total of 24, 22 and 8 endogenous metabolites tentatively identified in liver, brain and plasma, respectively, were significantly changed in venlafaxine exposed meagre, showing tissue-dependent variations in the metabolic profile. The amino acids tryptophan, tyrosine and phenylalanine, which are related to the synthesis, availability, and expression of neurotransmitters (e.g., serotonin, dopamine, epinephrine), showed to be dysregulated by venlafaxine exposure. A high impact was observed in fish brain metabolome that showed a trend of up-regulation for most of the tentatively identified metabolites. In conclusion, the identification of possible biomarkers of exposure in fish metabolome to environmental stressors such as venlafaxine is crucial to assess early signal changes at molecular level, enabling the prevention of deleterious effects at the organism and population levels., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Bisphenol A (BPA) is one of the main ubiquitous compounds released from plastics in the environment. This compound, considered an endocrine disruptor, poses a risk to aquatic wildlife and human population, being included in multiple environmental monitoring programmes. Following the regulations restricting BPA use in the last years, BPA-like chemicals have been produced and used as BPA substitutes. However, they are not commonly included in monitoring programs yet and their presence is thus misrepresented, despite showing similar endocrine disrupting potential. In this work, an analytical method for analysing bisphenol A and five of its analogues (Bisphenol S, B, F, AF and Tetrabromobisphenol A) is described, validated for water (riverine, sea and wastewater), sediment, and biota (fish and biofilm) and applied to monitor their presence in the Ebro River Delta (NE Spain). In addition, plastic litter was also collected to evaluate their role as potential source of bisphenols. All compounds except BPF were detected in the analysed samples. Wastewater treatment plants (WWTPs) were discarded as major sources of BPs into the natural aquatic environment, as no BPs were detected in treated effluents. Indeed, the high levels of BPs in the natural environment could be related with direct discharge of raw wastewater from small rural population nucleus. The analysis of riverine plastic leachates yielded 4 out of the 6 BPs analysed, strengthening the hypothesis that plastic debris are also a source of BPs in the natural environment. Whereas Bisphenol S and BPA were detected in water and, to a limited extent, in biota, less polar analogues (mainly BPAF and TBBPA) were not found in any of the water samples. Instead, these hydrophobic BPs were found in fish tissues and biofilm, pointing out plastics and microplastics as their possible vectors. Finally, biofilm demonstrated its potential as sentinel of chemical contamination in freshwater environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

In this study, we evaluated the distribution of up to forty-three antibiotics and 4 metabolites residues in different environmental compartments of an urban river receiving both diffuse and point sources of pollution. This is the first study to assess the fate of different antibiotic families in water, biofilms and sediments simultaneously under a real urban river scenario. Solid phase extraction, bead-beating disruption and pressurized liquid extraction were applied for sample preparation of water, biofilm and sediment respectively, followed by the quantification of target antibiotics by UPLC-ESI-MS/MS. Twelve antibiotics belonging to eight chemical families were detected in Suquía River samples (67% positive samples). Sites downstream the WWTP discharge were the most polluted ones. Concentrations of positive samples ranged 0.003-0.29 µg L -1 in water (max. cephalexin), 2-652 µg kg -1 d.w. in biofilm (max. ciprofloxacin) and 2-34 µg kg -1 d.w. in sediment (max. ofloxacin). Fluoroquinolones, macrolides and trimethoprim were the most frequently detected antibiotics in the three compartments. However cephalexin was the prevalent antibiotic in water. Antibiotics exhibited preference for their accumulation from water into biofilms rather than in sediments (bioaccumulation factors > 1,000 L kg -1 d.w. in biofilms, while pseudo-partition coefficients in sediments < 1,000 L kg -1 d.w. ). Downstream the WWTP there was an association of antibiotics levels in biofilms with ash-free dry weight, opposite to chlorophyll-a (indicative of heterotrophic communities). Cephalexin and clarithromycin in river water were found to pose high risk for the aquatic ecosystem, while ciprofloxacin presented high risk for development of antimicrobial resistance. This study contributes to the understanding of the fate and distribution of antibiotic pollution in urban rivers, reveals biofilm accumulation as an important environmental fate, and calls for attention to government authorities to manage identified highly risk antibiotics., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019. Published by Elsevier B.V.)

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 C 60 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 C 60 fullerene and its main transformation product, [6,6]C 60 O epoxide, were studied to the mentioned organisms employing analyses by liquid chromatography coupled to high-resolution mass spectrometry. Our results show that C 60 fullerene and its [6,6]C 60 O present a low bioconcentration factor (BCF) to biofilms: BCF C60  = 1.34 ± 0.95 L/kg dw and BCF C60O  = 1.43 ± 0.72 L/kg dw . 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]C 60 O 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 C 60 fullerenes in their organism (BAF C60  = 2670 ± 3070 L/kg dw ; BAF C60O  = 1330 ± 1680 L/kg dw ), 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., (Copyright © 2019 Elsevier Inc. All rights reserved.)

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 (C 60 ) 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 C 60 on the studied endpoints, except for the accumulation of C 60 in R. balthica in TCS + C 60 treatment, which was lower than when the fullerenes were alone. Neither TCS nor C 60 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 C 60 (16.15 ± 1.67 and 18.9 ± 4.01 eggs/egg mass in TCS and TCS + C 60 treatments, respectively, vs. 13.17 ± 4.01 in control). The presence of C 60 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 C 60 and TCS + C 60 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 C 60 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 C 60 , 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., (Copyright © 2019 Elsevier Inc. All rights reserved.)

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., (Copyright © 2019. Published by Elsevier B.V.)

Due to their diverse applications, gold nanoparticles (AuNPs) are expected to increase of in the environment, although few studies are available on their mode of action in aquatic organisms. The genotoxicity of AuNPs, alone or combined with the human pharmaceutical gemfibrozil (GEM), an environmental contaminant frequently detected in aquatic systems, including in marine ecosystems, was examined using gilthead seabream erythrocytes as a model system. Fish were exposed for 96 h to 4, 80 and 1600 μg L -1 of 40 nm AuNPs with two coatings - citrate or polyvinylpyrrolidone; GEM (150 μg L -1 ); and a combination of AuNPs and GEM (80 μg L -1 AuNPs + 150 μg L -1 GEM). AuNPs induced DNA damage and increased nuclear abnormalities levels, with coating showing an important role in the toxicity of AuNPs to fish. The combined exposures of AuNPs and GEM produced an antagonistic response, with observed toxic effects in the mixtures being lower than the predicted. The results raise concern about the safety of AuNPs and demonstrate interactions between them and other contaminants., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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 (C 60 ) 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 C 60 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 C 60 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., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Gold nanoparticles (AuNPs) are found in a wide range of applications and therefore expected to present increasing levels in the environment. There is however limited knowledge concerning the potential toxicity of AuNPs as well as their combined effects with other pollutants. Hence, the present study aimed to investigate the effects of AuNPs alone and combined with the pharmaceutical gemfibrozil (GEM) on different biological responses (behaviour, neurotransmission, biotransformation and oxidative stress) in one of the most consumed fish in southern Europe, the seabream Sparus aurata. Fish were exposed for 96 h to waterborne 40 nm AuNPs with two coatings - citrate and polyvinylpyrrolidone (PVP), alone or combined with GEM. Antioxidant defences were induced in liver and gills upon both AuNPs exposure. Decreased swimming performance (1600 μg.L -1 ) and oxidative damage in gills (4 and 80 μg.L -1 ) were observed following exposure to polyvinylpyrrolidone coated gold nanoparticles (PVP-AuNPs). Generally, accumulation of gold in fish tissues and deleterious effects in S. aurata were higher for PVP-AuNPs than for cAuNPs exposures. Although AuNPs and GEM combined effects in gills were generally low, in liver, they were higher than the predicted. The accumulation and effects of AuNPs showed to be dependent on the size, coating, surface charge and aggregation/agglomeration state of nanoparticles. Additionally, it was tissue' specific and dependent on the presence of other contaminants. Although, gold intake by humans is expected to not exceed the estimated tolerable daily intake, it is highly recommended to keep it on track due to the increasing use of AuNPs., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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 pCO 2 levels (ΔpCO 2 ∼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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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] ~20μgL -1 ) and via dietary sources ([VFX] ~160μgkg -1 dry weight), as well as to increased temperature (ΔT°C=+5°C) and high CO 2 levels (ΔpCO 2 ~1000μatm; equivalent to ΔpH=-0.4units). 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., (Copyright © 2018. Published by Elsevier B.V.)

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 C 60 ) are good adsorbents of organic contaminants and their interaction can potentially affect their toxicity to river biofilms. We tested the C 60 interactions with selected OMCs and their effects on river biofilms in different short-term experiments. In these, river biofilms were exposed to C 60 and three OMCs (triclosan, diuron, or venlafaxine) and their respective mixtures with fullerenes (C 60 + each OMC). The effects were evaluated on structural, molecular, and functional descriptors of river biofilms. Our results showed that C 60 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 C 60 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 C 60, and to the possible competition between C 60 pollutants on blocking the receptors of the biological cell membranes. We conclude that the presence of C 60 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.

Lipid regulators are among the most prescribed human pharmaceuticals worldwide. Gemfibrozil, which belongs to this class of pharmaceuticals, is one of the most frequently encountered in the aquatic environment. However, there is limited information concerning the mechanisms involved in gemfibrozil effects to aquatic organisms, particularly to marine organisms. Based on this knowledge gap, the current study aimed to assess biochemical and behavioral effects following a sublethal exposure to gemfibrozil (1.5, 15, 150, 1500 and 15,000 μg L -1 ) in the estuarine/marine fish Sparus aurata. After the exposure to 1.5 μg L -1 of gemfibrozil, fish had reduced ability to swim against a water flow and increased lipid peroxidation in the liver. At concentrations between 15-15,000 μg L -1 , the activities of some enzymes involved in antioxidant defense were induced, appearing to be sufficient to prevent oxidative damage. Depending on the organ, different responses to gemfibrozil were displayed, with enzymes like catalase being more stimulated in gills, whereas glutathione peroxidase was more activated in liver. Although there were no obvious concentration-response relationships, the integrated biomarker response version 2 (IBRv2) analysis revealed that the highest concentrations of gemfibrozil (between 150-15,000 μg L -1 ) caused more alterations. All the tested concentrations of gemfibrozil induced effects in S. aurata, in terms of behavior and/or oxidative stress responses. Oxidative damage was found at a concentration that is considered environmentally relevant, suggesting a potential of this pharmaceutical to impact fish populations., (Copyright © 2018. Published by Elsevier B.V.)

Removal of emerging pollutants, such as pharmaceuticals, from wastewater is a challenge. Adsorption is a simple and efficient process that can be applied. Clays, which are natural and low-cost materials, have been investigated as adsorbent. In this work, raw vermiculite and its three modified forms (expanded, base, and acid/base treated) were tested for removal of a widely used antidepressant, venlafaxine. Adsorption kinetics followed Elovich's model for raw vermiculite while the pseudo-2nd order model was a better fit in the case of other materials. Equilibrium followed Langmuir's model for the raw and the acid/base-treated vermiculite, while Redlich-Peterson's model fitted better the expanded and the base-treated materials. The adsorption capacity of vermiculite was significantly influenced by the changes in the physical and chemical properties of the materials caused by the treatments. The base-treated, raw, and expanded vermiculites showed lower maximum adsorption capacities (i.e., 6.3 ± 0.5, 5.8 ± 0.7, 3.9 ± 0.2 mg g -1 , respectively) than the acid/base-treated material (33 ± 4 mg g -1 ). The acid/base-treated vermiculite exhibited good properties as a potential adsorbent for tertiary treatment of wastewater in treatment plants, in particular for cationic species as venlafaxine due to facilitation of diffusion of the species to the interlayer gallery upon such treatment. Graphical abstract ᅟ.

Widespread use of pharmaceuticals and suboptimal wastewater treatment have led to increased levels of these substances in aquatic ecosystems. Lipid-lowering drugs such as gemfibrozil, which are among the most abundant human pharmaceuticals in the environment, may have deleterious effects on aquatic organisms. We examined the genotoxicity of gemfibrozil in a fish species, the gilthead seabream (Sparus aurata), which is commercially important in southern Europe. Following 96-h waterborne exposure, molecular (erythrocyte DNA strand breaks) and cytogenetic (micronuclei and other nuclear abnormalities in cells) endpoints were measured. Gemfibrozil was positive in both endpoints, at environmentally relevant concentrations, a result that raises concerns about the potential genotoxic effects of the drug in recipient waters., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The aim of the present work was to develop and validate a multi-residue method for the analysis of 33 human and veterinary pharmaceuticals (non-steroidal anti-inflammatory drugs (NSAIDs)/analgesics, antibiotics and psychiatric drugs), including some of their metabolites, in several aqueous environmental matrices: drinking water, surface water and wastewaters. The method is based on solid phase extraction (SPE) followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) and it was validated for different aqueous matrices, namely bottled water, tap water, seawater, river water and wastewaters, showing recoveries between 50% and 112% for the majority of the target analytes. The developed analytical methodology allowed method detection limits in the low nanograms per liter level. Method intra- and inter-day precision was under 8% and 11%, respectively, expressed as relative standard deviation. The developed method was applied to the analysis of drinking water (bottled and tap water), surface waters (seawater and river water) and wastewaters (wastewater treatment plant (WWTP) influent and effluent). Due to the selectivity and sensitivity of the optimized method, it was possible to detect pharmaceuticals in all the aqueous environmental matrices considered, including in bottled water at concentrations up to 31ngL -1 (salicylic acid). In general, non-steroidal anti-inflammatory drugs/analgesics was the therapeutic group most frequently detected, with the highest concentrations found in wastewaters (acetaminophen and the metabolite carboxyibuprofen at levels up to 615 and 120μgL -1 , respectively)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The occurrence of 33 pharmaceuticals and metabolites was evaluated along the Lis river and in the influents and effluents of two wastewater treatment plants (WWTPs) located along the river. Results indicate that pharmaceuticals, such as ibuprofen, ketoprofen, carbamazepine and fluoxetine, and the metabolite salicylic acid are widespread along the Lis river, showing 100% of detection frequency, at levels up to 1.3μgL -1 . The number of molecules detected increased along the river, with 11 molecules in the source, 15 upstream WWTP 1, 16 downstream WWTP 1 and upstream WWTP 2 and 19 downstream WWTP 2. The highest concentrations were often found downstream near the river mouth. Different possible sources of contamination of the Lis river were identified, namely WWTP effluents, untreated wastewaters and livestock production. Nevertheless, the discharge of WWTP effluents appeared to be the most pronounced, given that, in general, it was noticed an increase in the concentration of pharmaceuticals downstream of the WWTPs. WWTP effluents contributed with a total mass load of pharmaceuticals into the Lis river between 470 and 2317mg/d/1000 inhabitants. Non-steroidal anti-inflammatory drugs/analgesics were the therapeutic group with a high contribution to the total mass load of pharmaceuticals entering the Lis river, followed by psychiatric drugs and antibiotics. No seasonal variation was observed for the detected concentrations of pharmaceuticals. At the levels detected in the Lis river, sulfamethoxazole, clarithromycin, azithromycin and ibuprofen showed to have potential risk for aquatic organisms. These findings show that further studies embracing different environmental compartments (water, sediment and biota) are needed, in order to evaluate the partition/distribution of pharmaceuticals, their metabolites and transformation products in the environment as well as to predict their possible impact to non-target organisms and, in a last instance, to human health., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Pharmaceuticals have been identified as environmental emerging pollutants and are present in different compartments, including soils. Chemical remediation showed to be a good and suitable approach for soil remediation, though the knowledge in their impact for terrestrial organisms is still limited. Therefore, in this work, two different chemical remediation treatments (Fenton oxidation and nanoremediation) were applied to a soil contaminated with an environmental representative concentration of ibuprofen (3 ng g(-1)). The phytotoxic impact of a traditional soil remediation treatment (Fenton oxidation) and of a new and more sustainable approach for soil remediation (nanoremediation using green nano-scale zero-valent iron nanoparticles (nZVIs)) was evaluated in Lactuca sativa seeds. Percentage of seed germination, root elongation, shoot length and leaf length were considered as endpoints to assess the possible acute phytotoxicity of the soil remediation treatments as well as of the ibuprofen contaminated soil. Both chemical remediation treatments showed to have a negative impact in the germination and development of lettuce seeds, exhibiting a reduction up to 45% in the percentage of seed germination and a decrease around 80% in root elongation comparatively to the contaminated soil. These results indicate that chemical soil remediation treatments could be more prejudicial for terrestrial organisms than contaminated soils., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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 0.01ngg(-1) to 2.08ngg(-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 26.4ngg(-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., (Copyright © 2016 Elsevier B.V. All rights reserved.)