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Wastewaters are considered one of the main sources of pollution in the aquatic environment as release a large number of contaminants every day. Emerging contaminants such as pharmaceuticals have special interest due to the high levels of consumption by the global population, their bioactive properties and because actual directives do not include the monitoring of pharmaceuticals. Moreover, it is well-known that pharmaceuticals can be degraded to metabolites or transformation products (TPs), which could be more toxic than the parental compound. In this study, we have developed an analytical method based on solid-phase extraction (SPE) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) to determine 76 highly consumed pharmaceuticals, including metabolites and TPs in wastewater effluents. In the 10 wastewaters analysed, the mean concentrations were in the µg L−1 levels, being mycophenolic acid, levodopa, ibuprofen, 4-aminoantypirine, losartan, amylmetacresol, amoxicillin, fluticasone, tramadol, budesonide, chlorpheniramine and diclofenac the pharmaceuticals with the highest concentrations. This study provides a comprehensive optimization on the MS conditions to determine pharmaceutical compounds and their metabolites and provides a spectral characterization to be used for the identification of these compounds in water. ; This research was funded by Universitat Ramon Llull (project 2021-URL-Proj-024; C.G.-C.) and the Spanish Government (PID2020-113371RA-C22; C.G-C and PID2019-105732GB-C21, S.L.). ; Peer reviewed

Metabolic changes of Daphnia magna pools due different abiotic factors linked to global climate change (salinity, temperature and hypoxia) were investigated using untargeted GC–MS and advanced chemometric strategies using a three factors two-level full factorial experimental design (DoE). Effects of these three factors and identity of the metabolites whose concentrations changed because of them were investigated. The simultaneous analysis of GC–MS data sets using Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) allowed the resolution of the elution and mass spectra profiles of a large number of D. magna metabolites. Changes in peak areas of these metabolites were then analyzed by Principal Component Analysis (PCA), by ANOVA-Simultaneous Component Analysis (ASCA) and by Orthogonal Partial Least Squares-Discriminant Analysis (OPLS-DA), and the combined effects of the three investigated stressors were assessed. Results confirmed the strong influence of increasing environmental salinity levels on the D. magna metabolome. This impact was specially highlighted by changes on the cellular content of carbohydrates, fatty acids, organic acids and amino acid molecules. In contrast, these effects were less significant for the other two factors (temperature and hypoxia) at the moderate stressing experimental conditions investigated in this work when they were not combined with salinity. ; The research leading to these results received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 320737. ; Peer reviewed

Introduction: Climate change is a major concern for the scientific community, demanding novel information about the effects of environmental stressors on living organisms. Metabolic profiling is required for achieving the most extensive possible range of compounds and their concentration changes on stressed conditions. Objectives: Individuals of the crustacean species Daphnia magna were exposed to three different abiotic factors linked to global climate change: high salinity, high temperature levels and hypoxia. Advanced chemometric tools were used to characterize the metabolites affected by the exposure. Method: An exploratory analysis of gas chromatography-mass spectrometry (GC–MS) data was performed to discriminate between control and exposed daphnid samples. Due to the complexity of these GC–MS data sets, a comprehensive untargeted analysis of the full scan data was performed using multivariate curve resolution-alternating least squares (MCR-ALS) method. This approach enabled to resolve most of the metabolite signals from interference peaks caused by derivatization reactions. Metabolites with significant changes in their peak areas were tentatively identified and the involved metabolic pathways explored. Results: D. magna metabolic biomarkers are proposed for the considered physical factors. Metabolites related with energy metabolic pathways including some amino acids, carbohydrates, organic acids and nucleosides were identified as potential biomarkers of the investigated treatments. Conclusions: The proposed untargeted GC–MS metabolomics strategy and multivariate data analysis tools were useful to investigate D. magna metabolome under environmental stressed conditions. © 2016, Springer Science+Business Media New York. ; The research leading to these results received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013) / ERC Grant Agreement no. 320737. ; Peer reviewed

The objective of the present study is to evaluate the presence, seasonal variability and impact of plastic additives along the Besos river basin (Catalonia, Spain). This river flows through a highly urbanized and industrialized area with discharge of >25 Wastewater Treatment Plants (WWTPs) and with large amounts of floating plastics. Compounds studied included 5 phthalates, its substitutes acetyl tributyl citrate (ATBC) and bis(2-ehtylhexyl) adipate, 12 long and short chain alkylphenols, bisphenol A and benzophenone, most of them high volume production chemicals. High-performance liquid chromatography-tandem mass spectrometry (HPLC-MS) was used to determine ng/L concentrations. Toxicity evaluation was performed for each individual compound using Daphnia magna as test organism and it was found that the effect concentration (EC50) decreased with increasing octanol-water partition coefficients. The EC50 values calculated and Measured Environmental Concentrations were used to determine the risk quotients. Only diethylhexylphthalate, nonylphenol and octylphenol, with median concentrations from 41.9 to 826 ng/L, caused a small risk mostly in downstream waters with 50-75% of the samples overpassing the Environmental Quality Standards set by the European Union. Seasonal variations were observed with higher levels in summer due to low water flows. WWTPs effluents and leaching from floating plastics or microplastics were presumably main sources of pollution. ; This work has been financed by the Ministry of Science and Innovation of Spain under the project PID 2019-105732 GB-C21. ; Peer reviewed

The performances of gas chromatography with mass spectrometry and of comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry are examined through the comparison of Daphnia magna metabolic profiles. Gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with mass spectrometry were used to compare the concentration changes of metabolites under saline conditions. In this regard, a chemometric strategy based on wavelet compression and multivariate curve resolution–alternating least squares is used to compare the performances of gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry for the untargeted metabolic profiling of Daphnia magna in control and salinity-exposed samples. Examination of the results confirmed the outperformance of comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry over gas chromatography with mass spectrometry for the detection of metabolites in D. magna samples. The peak areas of multivariate curve resolution–alternating least squares resolved elution profiles in every sample analyzed by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry were arranged in a new data matrix that was then modeled by partial least squares discriminant analysis. The control and salt-exposed daphnids samples were discriminated and the most relevant metabolites were estimated using variable importance in projection and selectivity ratio values. Salinity de-regulated 18 metabolites from metabolic pathways involved in protein translation, transmembrane cell transport, carbon metabolism, secondary metabolism, glycolysis, and osmoregulation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ; Hadi Parastar would like to thank Sharif University of Technology (SUT) of Iran for financial support for a short sabbatical leave at IDAEA-CSIC. The research leading to these results received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013) / ERC Grant Agreement no. 320737 ; Peer reviewed

Gull eggs are excellent bioindicators of environmental pollution as reflect the contamination levels of coastal areas, especially of persistent and bioacumulative compounds such as perfluoroalkyl substances (PFAS). This study aims to evaluate the geographical distribution and 10-year temporal trends (2009-2018) of 17 PFAS in eggs of two gull species (Larus michahellis and Larus audouinii) from 5 main Spanish colonies. ∑PFAS ranged from 13.7 ± 5.9 to 164 ± 17 ng g-1 wet weight and higher concentrations were observed in L. audouinii than in L. michahellis. Perfluorooctane sulfonate (PFOS) was the predominant compound in all samples, followed by perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTriDA). Perfluorododecanoic acid (PFDoA), perfluorodecanoic acid (PFDA) and perfluorooctanoic acid (PFNA) were also found in all studied areas but at lower concentrations, while perfluorooctanoic acid (PFOA) was only detected in the Medes Islands. Principal Component Analysis revealed the co-occurrence of the 6 detected PFAS, and differentiated samples from Ebro Delta and Medes Islands, both located in the North-Eastern Mediterranean Sea, with high contribution of all PFAS, from Chafarinas and Atlantic Islands with lower concentration levels and variability. Also, different patterns were observed among colonies, suggesting the fish-based diet plays an important role in PFAS bioaccumulation. In all colonies, except for the Medes Islands, ∑PFAS decreased through the 10-year study period, with PFOS, PFUnA, and PFTriDA showing a significant concentration reduction in a colony-specific manner. This study demonstrates the usefulness and importance of continuous systematic long-term monitoring to determine the geographical distribution and temporal variations of PFAS in marine protected areas using gull eggs as bioindicators of environmental pollution. ; We acknowledge the Islas Atlánticas National Park, Refugio de Caza de las Islas Chafarinas, Delta de l'Ebre Natural Park, and Montgrí, les Illes Medes i el Baix Ter Natural Park to authorize sampling for our work. The Servei de Protecció i Gestió de la Fauna (Catalan Government) is acknowledged for sampling permission. We are especially grateful to José Antonio Fernández-Bouza and Vicente Piorno (Atlantic Islands), Javier Zapata (Chafarinas) for organizing the sampling, logistic support and transport of samples and for their valuable contributions to the study, and Mònica Cárdenas and Marc Bosch (Medes Islands) and Francesc Vidal and Antoni Curcó (PN Delta de l'Ebre) for facilitating sampling. We also thank Carles Domingo and Julia Piccardo (Forestal Catalana) for valuable field assistance. This research has been funded by the Spanish Autonomous Organism of National Parks (projects 038/2009 and 2012/768) and by the Spanish Ministry of Science and Innovation [PID 2019-105732 GB-C21, MCIN/AEI/10.13039/501100011033. ; Peer reviewed

11 páginas.-- 2 tablas.-- 3 figuras.-- 61 referencias ; A decontamination technique based in cyclodextrin extraction has been developed to eliminate nonylphenol (NP) and 16 polycyclic aromatic hydrocarbons (PAHs; the US Environmental Protection Agency priority pollutants list) from sewage sludge. In a first step, PAHs and NP were characterised in six sludges to determine contamination levels according to limit values proposed by the European Union Sludge Directive draft. There were few variations in the total PAHs content with levels of 1.88 to 3.05 mg kg-1. Three-ring PAHs predominated, but fluoranthene and pyrene were also present. None of the sludge exceeded the PAHs limit proposed by the European Union's draft Directive. On the contrary, NP content in four of the six sludges was over the recommended limits of 50 mg kg-1 for NP ethoxylates. With the aim of obtaining NP values below the concentration limits proposed to use the sewage sludge as agricultural amendments, a preliminary study using hydroxypropyl-β-cyclodextrin (HPBCD) extractions as a decontamination technique was carried out. About 90 % of NP content was removed with only one extraction with HPBCD, whereas after three sequential extractions using an aqueous solution without HPBCD, the NP extraction percentage was less than 1 %. Simultaneously, PAHs extraction percentages obtained with HPBCD were also much higher than when aqueous solution was used, especially in the case of two- and three-ring PAHs. Finally, the potential environmental hazard of HPBCD leachates to aquatic organisms (Daphnia magna) was tested. These results indicate that the treatment of sewage sludge with cyclodextrin could allow their safe use as fertiliser in agriculture. © 2013 Springer-Verlag Berlin Heidelberg. ; Support from projects CTM2006-04626 and CTM2009-07335, Spanish Ministry of Science and Innovation (cofunded by Fondo Europeo de Desarrollo Regional, FEDER), are greatly appreciated. M.A. Sánchez-Trujillo acknowledges a research contract from Consejo Superior de Investigaciones Científicas (CSIC, JAEPre 0800763) cofinanced by Fondo Social Europeo (FSE). ; Peer Reviewed

This study provides new knowledge on the mobility, behavior, and partitioning of 17 perfluoroalkyl substances (PFASs) in the water-sediment-plant system along the Dongzhulong and Xiaoqing Rivers. The fate of PFASs in these rivers is also discussed. The study area is affected by the industrial production of perfluorooctanoic acid (PFOA). The ∑PFASs in water and sediments close to the industrial discharge were 84,000 ± 2000 ng/L and 2300 ± 200 ng/g dw, respectively, with the concentrations decreasing along the river due to dilution. PFOA was the dominant compound (74–97% of the ∑PFASs), although other PFASs were identified close to urban areas. Principal component analysis and solid-liquid distribution coefficients revealed that long-chain PFASs accumulated in the sediment whereas short-chain PFASs remained in the water all along the river. PFASs were taken up by plants and remobilized to different plant compartments according to shoot concentration factors (SCFs), root concentration factors (RCF), and transfer factors (TFs). Among the four plant species studied, floating plants absorbed high levels of PFASs, while rooted species translocated short-chain PFASs from the roots to the shoots. Therefore, floating species, due to their high uptake capacity and large proliferation rate, could eventually be used for phytoremediation. ; Pere Colomer Vidal acknowledges the funding from the European Union Europe Aid 'SEW-REAP' project [ECRIP ICI+/2014/348–010]. The Spanish Ministry of Science and Innovation under the grant PID2019–105732GB-C21 and the Local Innovative and Research Teams Project of the Guangdong Pearl River Talents Program (2017BT01Z134) provided financial support. Dr. Chunling Luo would like to thank the support from the Ten Thousand Talent Program of the Organization Department of the Central Committee of the CPC. This work was carried out at the facilities of the Guangzhou Institute of Geochemistry. ; Peer reviewed

Neuro-active pharmaceuticals have been reported to act as endocrine disruptors enhancing reproduction in the model crustacean Daphnia manga at environmental concentrations of ng/L. Oxylipins and more specifically eicosanoids, which are lipid mediators formed from polyunsaturated fatty acids (PUFAs), are known to regulate reproduction together with other physiological processes in insects. In D. magna, the biosynthesis of eicosanoids and their putative role in the regulation of reproduction has been studied using transcriptomics, genomics and exposures to cyclooxygenase inhibitors. Quantification of eicosanoids and oxylipins derived from PUFAs upon exposure to pharmaceuticals is therefore crucial for a better understanding of the mode of action of neuro-active pharmaceuticals on aquatic invertebrates. The aim of this study was to investigate shifts in the oxylipin profile in D. magna adults upon exposure to environmental concentrations of the three psychiatric drugs, fluoxetine, diazepam and carbamazepine, with known effects of enhancing offspring production. Oxylipin profiles were determined in whole organism tissues using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Up to 28 different oxylipins belonging to arachidonic (AA), linoleic acid (LA), α-linoleic acid (α-LA) and eicosapentaenoic acid (EPA) pathways were detected and quantified in D. magna adults. Exposure to the selected psychiatric drugs showed that fluoxetine enhanced the accumulation of the cyclooxygenase (COX) product 12-hydroxyheptadecatrienoic acid (12-HHTrE), whereas diazepam increased the concentration of eicosanoids belonging to the lipoxygenase (LOX) and cytochrome P450 (CYP) pathways (HETEs, EpOMEs, HODEs, HOTrEs and HEPEs) from the AA, LA, αLA and EPA pathways. Carbamazepine had little effect and only one LA-derived compound from the LOX pathway (13-HODE) increased significantly. This means that despite having different modes of action in humans, fluoxetine and diazepam up-regulated eicosanoid pathways in D. magna, closely related to known biologically active products that regulate reproduction in insects. © 2018 Elsevier B.V. ; The research leading to these results received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013) / ERC Grant Agreement no. 320737 and the Spanish project (CTM2017-83242-R). ; Peer reviewed

There is a growing concern about the occurrence of bisphenols and benzophenone UV filters in natural ecosystems, while data are limited regarding their actual occurrence in wildlife species, especially in raptors. In this study, concentrations of bisphenol and benzophenone UV filter analogues were determined in liver tissue samples (n = 38) from white-tailed eagles (Haliaeetus albicilla) that were found dead in Smøla (2006-2018), which is a Norwegian municipality that holds one of the densest breeding populations of white-tailed eagles in Europe. Bisphenol AF (BPAF; a fluorinated analogue) was the most ubiquitous contaminant since it was detected in 32 liver samples at concentrations ranging from 1.08 to 6.68 ng/g wet weight (w.w.), followed by bisphenol A (BPA, mean 10.4 ng/g w.w.), benzophenone-1 (BzP-1, mean 3.24 ng/g w.w.), and 4-hydroxybenzophenone (4-OH-BzP, mean 0.62 ng/g w.w.). The concentrations found in livers suggested that white-tailed eagles potentially accumulate bisphenols and benzophenone UV filters, which raises concern, as these plastic and personal care product-related emerging contaminants can show endocrine-disrupting properties. The high detection frequency of the fluorinated BPAF warrants further attention as other fluorinated compounds have proven to be extremely persistent and potentially harmful to wildlife. ; his project was supported financially by the Departments of Chemistry and Biology at the Norwegian University of Science and Technology (NTNU), and the Uniform—Foundation for Funds and Legislation through the "Anders Jahre's Foundation for the Advancement of Science (Chemical and Marine Technology)". All samples were indexed and stored by the Department of Biology and chemical analysis was conducted at the Department of Chemistry, NTNU. BON acknowledges the promotion of the young employment and implantation of the "Subprograma Estatal de Incorporación, del Programa Estatal de Promoción del Talento y su Empleabilidad en I+D+I" in the frame of the "Programa Operativo Empleo Juvenil 2014–2020", from "Iniciativa de Empleo Juvenil y el Fondo Social Europeo" under the project MIN19_CAT_IDAEA_001. SL and BON acknowledge the Ministry of Science and Innovation of Spain for the project PID2019-105732GB-C21. ; Peer reviewed

With rising environmental levels of carbon-based nanoparticles (CBNs), there is an urgent need to develop an understanding of their biological effects in order to generate appropriate risk assessment strategies. Herein, we exposed zebrafish via their diet to one of four different CBNs: C60 fullerene (C60), single-walled carbon nanotubes (SWCNT), short multi-walled carbon nanotubes (MWCNTs) or long MWCNTs. Lipid alterations in male and female zebrafish were explored post-exposure in three target tissues (brain, gonads and gastrointestinal tract) using 'omic' procedures based in liquid chromatography coupled with mass spectrometry (LC-MS) data files. These tissues were chosen as they are often target tissues following environmental exposure. Marked alterations in lipid species are noted in all three tissues. To further explore CBN-induced brain alterations, Raman microspectroscopy analysis of lipid extracts was conducted. Marked lipid alterations are observed with males responding differently to females; in addition, there also appears to be consistent elevations in global genomic methylation. This latter observation is most profound in female zebrafish brain tissues post-exposure to short MWCNTs or SWCNTs (P < 0.05). This study demonstrates that even at low levels, CBNs are capable of inducing significant cellular and genomic modifications in a range of tissues. Such alterations could result in modified susceptibility to other influences such as environmental exposures, pathology and, in the case of brain, developmental alterations. © The Author 2016. ; The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC grant agreement no. 320737. One of the first authors (E.G.) acknowledges the Spanish Government (Ministerio de Educación, Cultura y Deporte) for a predoctoral FPU scholarship (FPU13/04384). Research in F.L.M.'s laboratory is supported by Rosemere Cancer Foundation and the Engineering and Physical Sciences Research Council (EPSRC; grant no: EP/K023349/1). Data relating to this study is deposited and freely available at: https://dx.doi.org/10.6084/m9.figshare.4012683.v1. ; Peer reviewed