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Pollution has been less investigated in marine and coastal environments than in inland waters. The low levels at which pollutants are expected to be present in seawater calls for the use of reliable and high sensitivity analytical methodologies. In this context, this work presents the optimization and validation of an analytical method to determine 26 medium to highly polar pesticides in seawater based on solid phase extraction and liquid chromatography-tandem mass spectrometry detection. The developed methodology was linear, accurate (relative recoveries within 80–120% for most analytes), repeatable (relative standard deviations, This work has been financially supported by the EU FP7 through the SOLUTIONS project (FP7-ENV-2013, No. 603437), by the Ministry of Science, Innovation and Universities through the PLAS-MED project (CTM2017-89701C3-R), and by the Generalitat de Catalunya (Consolidated Research Group 2017 SGR 01404 - Water and Soil Quality Unit). Thanks to the Swedish University of Agricultural Sciences for its support through the August T Larsson Guest Researcher Programme. The authors would also like to express their gratitude to Cristina Bosch, Gabriella Schirinzi, Josep Sanchís, Mar Olmos and Samuel Jimenez for their assistance with sampling, and to Simon Monllor for his assistance with sample processing.

This study analyses the presence of 17 cytostatic agents from seven different groups, based on their different mechanisms of action, in the effluent from a medium-sized hospital located in eastern Spain. Analysis of the compounds found in the effluents studied involved solidphase extraction (SPE) coupled on-line to a high performance liquid chromatograph tandem mass spectrometer (HPLC-MS/MS). The environmental risk of the compounds studied was then assessed by calculating the hazard quotient (HQ), combining the measured environmental concentrations (MECs) with dose-response data based on the predicted no effect concentrations (PNECs). In addition, the environmental hazard associated was evaluated in accordance with their intrinsic characteristics by calculating the PBT (Persistence Bioaccumulation Toxicity) index. The results of this study showed the presence of seven of the 17 compounds analysed in a range of between 25 and 4761 ng/L. The highest concentrations corresponded to ifosfamide (58-4761 ng/L), methotrexate (394-4756 ng/L) and cyclophosphamide (46-3000 ng/L). Assessment of the environmental hazard showed that the three hormonal agents (tamoxifen and its metabolites endoxifen and hydroxytamoxifen) exhibited a maximum PBT value of 9 due to their inherent harm to the environment resulting from their characteristics of persistence, bioaccumulation and toxicity. A combined evaluation of the risk and environmental hazard showed that three of the 17 compounds studied, namely, ifosfamide, imatinib and irinotecan, all of which exhibited HQ values higher than 10 and PBT indices of 6, indicative of a particularly high potential to harm the environment, deserve special attention.

The development of quantitative and qualitative analytical methods to assess micro-plastics (MPLs) and nano-plastics (NPLs) content in the environment is a central issue for realistic risk assessment studies. However, the quantitative analysis continues being a critical issue, in particular for MPLs from 100 μm down to the nano-sized range in complex environmental samples. This paper evaluates the potential of mass spectrometry for the analysis of MPLs and NPLs. The performance of different techniques including matrix-assisted laser desorption ionisation (MALDI) coupled to time-of-flight mass spectrometry (TOF-MS), liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS), and the ambient ionisation approaches as desorption electrospray ionisation (DESI) and direct analysis real-time (DART), were assessed for the study of polystyrene (PS) MPLs and NPLs in natural waters. A method based on LC-HRMS, equipped with an atmospheric pressure photoionisation source (APPI), operated in negative conditions for the quantitative analysis of PS MPLs and NPLs in natural waters, was developed. The chromatographic separation was achieved using an advanced polymer chromatographic (APC) column using toluene isocratic as the mobile phase. The optimal analytical method showed an instrumental limit of detection (ILOD) of 20 pg and methods limits of detection and quantification around 30 pg L−1 and 100 pg L−1, respectively. And, recoveries of 60 and 70% in samples from rivers and the marine coast, respectively. The performance of the new method was proved by the analysis of fortified samples and natural seawater samples. © 2019, This study was funded by the Ministry of Economy and Competitiveness through the project PLAS-MED (CTM 2017-89701C3-1-R). G. Schirinzi thanks her fellowship BES-2015-072281 and M. Llorca postdoctoral fellowship JCI-2014-21736. The authors express their deepest gratitude to R. Chaler and D. Fanjul for their technical support during the high-performance LC–HRMS analysis, M. Martinez to supply PS industrial polymer and C. Quero for the support during MALDI-TOF/MS analysis.

We used the freshwater insect Hydropsyche sp. to investigate the impact of diets lacking arachidonic acid (ARA) and an environmentally relevant mixture of NSAIDs (Ibuprofen, Ketoprofen, Diclofenac and Naproxen at a nominal concentration of all compounds together 16.75 μg L) on their metabolism of ARA and prostaglandins (PGs). The organisms were exposed for 16 days to four different treatments: a reference (FF), a diet lacking ARA (O), to NSAIDs in water (FFN) and to the combination of the two factors (ON). Mortality, biomass and bioconcentration of pharmaceuticals were investigated. The ARA and PGs levels in the organisms were monitored by utilising a targeted metabolomics approach. NSAIDs or dietary constraints did not produce significant differences in biomass or mortality of Hydropsyche sp. among treatments. In organisms exposed to NSAIDs, all pharmaceuticals were detected, except for Ketoprofen. Metabolomic approach determined the presence of PGH, PGE and PGD. Levels of ARA diminished significantly in those organisms in treatment ON. The levels of PGs responded negatively to the absence of ARA in diet: PGH diminished significantly with respect to the reference in treatment O while PGE diminished significantly in treatment ON. Regarding the effects of NSAIDs on ARA metabolism, our results suggest that it was sensitive to NSAIDs, but effects were weak and did not imply a general decrease in the PGs. We confirmed that ARA was the main substrate for the synthesis of PGs in Hydropsyche sp, their absence or poor levels of ARA in diet, produced changes in the PG levels., This work was supported by GLOBAQUA project (FP7, No 603629), the Spanish Ministry of Economy and Competitiveness through the projects CLIMALERT (PCIN-2017- 068) and SPACESTREAM (CGL 2017-88640-C2-1-R) and by the Generalitat de Catalunya (Consolidated Research Group “2014 SGR 291 – ICRA”). ICRA researchers thank funding from CERCA program. Julio C. López-Doval thanks the program Juan de la Cierva from the Spanish Ministry of Economy and Competitiveness (IJCI-2015-23644). Albert Serra-Compte benefits from an FI-DGR research fellowship from the Catalan Government (2016FI_B00601). Sara Rodriguez-Mozaz acknowledges the Ramon y Cajal program (RYC- 2014–16707) from the Spanish State Research Agency of Spanish Ministry of Science, Innovation and Universities (AEI-MCIU). Carmen Gutierrez Provecho and Juan David González-Trujillo (ICRA) are gratefully acknowledged for their assistance in the field collections and lab processing of the samples.

The emergence and spread of antibiotic resistance represents one of the most important public health concerns and has been linked to the widespread use of antibiotics in veterinary and human medicine. The overall elimination of antibiotics in conventional wastewater treatment plants is quite low; therefore, residual amounts of these compounds are continuously discharged to receiving surface waters, which may promote the emergence of antibiotic resistance. In this study, the ability of a fungal treatment as an alternative wastewater treatment for the elimination of forty-seven antibiotics belonging to seven different groups (β-lactams, fluoroquinolones, macrolides, metronidazoles, sulfonamides, tetracyclines, and trimethoprim) was evaluated. 77% of antibiotics were removed after the fungal treatment, which is higher than removal obtained in conventional treatment plants. Moreover, the effect of fungal treatment on the removal of some antibiotic resistance genes (ARGs) was evaluated. The fungal treatment was also efficient in removing ARGs, such as ermB (resistance to macrolides), tetW (resistance to tetracyclines), blaTEM (resistance to β-lactams), sulI (resistance to sulfonamides) and qnrS (reduced susceptibility to fluoroquinolones). However, it was not possible to establish a clear link between concentrations of antibiotics and corresponding ARGs in wastewater, which leads to the conclusion that there are other factors that should be taken into consideration besides the antibiotic concentrations that reach aquatic ecosystems in order to explain the emergence and spread of antibiotic resistance. © 2016 Elsevier Ltd., The authors wish to acknowledge the UAB veterinary hospital staff for their kindness permission and help for the samplings. This work has been funded by the Spanish Ministry of Economy and Competitiveness (projects CTM2013-48545-C2-2-R and JPIW2013-089-C02-02 ), co-financed by the European Union through the European Regional Development Fund (ERDF) and also supported by the Generalitat de Catalunya (Consolidated Research Groups 2014-SGR-476 and 2014-SGR-291 ). D. Lucas and M. Badia-Fabregat acknowledge the predoctoral grants from the Spanish Ministry of Education, Culture and Sports ( AP-2010-4926 ) and from UAB , respectively. J.L Balcazar and Sara Rodriguez-Mozaz acknowledge the Ramón y Cajal program ( RYC-2011-08154 and RYC-2014-16707 , respectively). Appendix A

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.

This study was aimed to determine the abundance of four antibiotic resistance genes (blaTEM, ermB, qnrS and sulI), as well as bacterial community composition associated with the intestinal mucus of wild freshwater fish species collected from the Foix and La Llosa del Cavall reservoirs, which represent ecosystems with high and low anthropogenic disturbance, respectively. Water and sediments from these reservoirs were also collected and analyzed to determine the pollution level by antibiotics. The blaTEM gene was only detected in brown trout and Ebro barbel, which were collected from La Llosa del Cavall reservoir. In contrast, the sulI and qnrS genes were only detected in common carp, which were collected from the Foix reservoir. Although the ermB gene was also detected in common carp, the values were below the limit of quantification. Likewise, water and sediment samples from the Foix reservoir had higher concentrations and more classes of antibiotics than those from La Llosa del Cavall. Pyrosequencing analysis of 16S rRNA genes revealed significant differences in bacterial communities associated with the intestinal mucus of fish species. Therefore, these findings suggest that anthropogenic activities are not only increasing the pollution of aquatic environments, but also contributing to the emergence and spread of antibiotic resistance in organisms that inhabit such environments.

This paper deals with urban groundwater contaminated with carbamazepine (CBZ) and five of its human metabolites in Barcelona. Groundwater samples were accordingly collected in the aquifers of Poble Sec and Besos River Delta. Higher concentrations and more compounds were found in the Besos River Delta aquifer, which is recharged by a river contaminated with treated effluent from numerous treatment plants. By contrast, the urban area of Poble Sec presented lower concentrations and fewer compounds. The results showed that CBZ could be attenuated in the Poble Sec aquifer since concentrations in groundwater were lower than those evaluated from mixing of the recharge sources. Conversely, CBZ and its human metabolites were not removed under the reducing conditions of the Besos River Delta aquifer probably because of the short residence time in this aquifer. (C) 2014 Elsevier Ltd. All rights reserved.

This work investigates, for the first time, the occurrence of 10 drugs of abuse, six metabolites, and three benzodiazepines in surface waters from the Jarama and Manzanares Rivers in the Madrid Region, the most densely populated area in Spain and one of the most densely populated in Europe. The results of this study have shown the presence of 14 out of the 19 compounds analyzed at concentrations ranging from 1.45 to 1020 ng L −1 . The most ubiquitous compounds, found in 100% of the samples, were the cocaine metabolite benzoylecgonine (BE), the amphetamine-like compound ephedrine (EPH), the opioids morphine (MOR), methadone (METH), and the METH metabolite 2-ethylene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), and the three investigated benzodiazepines alprazolam (ALP), diazepam (DIA) and lorazepam (LOR). Meanwhile, the largest concentrations observed corresponded to EPH (up to 1020 ng L −1 ), BE (823 ng L −1 ), EDDP (151 ng L −1 ), and LOR (167 ng L −1 ). The only not detected compounds were heroin (HER) and its metabolite 6-acetylmorphine (6ACM), lysergic acid diethylamide (LSD) and its metabolite 2-oxo-3-hydroxy-LSD (OH-LSD), and Δ 9 -tetrahydrocannabinol (THC). Overall, the levels measured are comparatively higher than those previously reported in Europe. Comparison of the results obtained for samples collected on different days (Thursday and Sunday) did not show meaningful differences between weekdays and weekends. The lack of (eco)toxicological data does not permit to predict or disregard potential adverse effects on wildlife. Risk assessment in humans would require further knowledge, not currently available, on exposure to these compounds through other routes like drinking water and/or food.

Antibiotics are emerging contaminants, which wing to their bioactivity, may lead to short-term and long-term alterations of natural microbial communities in aquatic environment. We investigated the effects of antibiotics on biofilm bacterial communities in the Llobregat River (Northeast Spain). Three sampling sites were selected: two less polluted sites and one hotspot. River water was collected from each site and used both as inoculum and medium for growing biofilms in independent mesocosms. After 25 d of biofilm colonization, we exposed the colonized biofilms to river waters from the downstream sites (progressively contaminated by antibiotics). A control from each site was maintained where the growing biofilm was always exposed to water from the same site. The bacterial community composition, bacterial live/dead ratio and extracellular enzyme activities of the biofilms were measured before and 9 d after exposing the biofilms to increasing contaminated waters. Sixteen antibiotic compounds were detected in the water from the three sampling sites. At each site, the antibiotics present in the highest concentrations were sulfonamides, followed by quinolones and macrolides. Bacterial communities of biofilms grown with the three river waters differed markedly in their structure, but less so in terms of functional descriptors. After switching the medium water to increasing pollution, biofilms exhibited increased levels of actinobacteria (HGC), a trend that was associated to the higher antibiotic concentrations in the water. These biofilms also showed increased bacterial mortality, and decreased extracellular leucine-aminopeptidase and alkaline phosphatase. There was a significant correlation between antibiotic concentrations and biofilm responses. Our results indicate that the continuous entrance of antibiotics in running waters cause significant structural and functional changes in microbial attached communities.

Concentrations of polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) were determined in two fish species, mullet (Mugil cephalus) and sea bass (Dicentrarchus labrax), collected from Bizerte Lagoon and the Mediterranean Sea. In all samples, PCBs were found in higher concentrations than OCPs. The highest concentrations of OCPs and PCBs were found in sea bass, and in Bizerte Lagoon. Concentrations of DDTs and PCBs detected in this study were generally comparable or slightly higher than those found in studies from other Mediterranean and non-Mediterranean regions subject to a high anthropogenic impact. ∑PCBs, ∑HCHs and HCB levels were negatively correlated with lipid content, while no such correlation was seen for ∑DDTs. A significant correlation between levels and length and between levels and weight existed only for ∑PCBs. The daily intake of PCBs and OCPs ingested by people living in Bizerte through the studied fish species was estimated and compared with those observed in other areas.

We used a short-term microcosm approach to investigate the influence of two different subinhibitory concentrations of ciprofloxacin (0.01 and 0.1 μg/ml) on both the abundance of a plasmid-mediated quinolone resistance determinant (qnrS) and the structure and composition of bacterial communities from impaired and pristine water supply reservoirs. The results showed that the abundance of the qnrS gene increases in water samples exposed to both subinhibitory concentrations of ciprofloxacin, especially in water samples from La Llosa del Cavall, which represents the pristine system. Subinhibitory ciprofloxacin concentrations also induced changes in bacterial community composition as indicated by the relative abundances of each operational taxonomic unit (OTU) across treatments. Therefore, our findings may be of significant importance because subinhibitory ciprofloxacin concentrations may promote antibiotic resistance and affect bacterial community composition in environmental settings.

Brominated flame retardants, including hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (PBDEs) are used to reduce the flammability of a multitude of electrical and electronic products, textiles and foams. The use of selected PBDEs has ceased, however, use of decaBDE and HBCD continues. While elevated concentrations of PBDEs in humans have been observed in Australia, no data is available on other BFRs such as HBCD. This study aimed to provide background HBCD concentrations from a representative sample of the Australian population and to assess temporal trends of HBCD and compare with PBDE concentrations over a 16 year period. Samples of human milk collected in Australia from 1993 to 2009, primarily from primiparae mothers were combined into 12 pools from 1993 (2 pools); 2001; 2002/2003 (4 pools); 2003/2004; 2006; 2007/2008 (2 pools); and 2009. Concentrations of ∑HBCD ranged from not quantified (nq) to 19 ng g −1 lipid while α-HBCD and γ-HBCD ranged from nq to 10 ng g −1 lipid and nq to 9.2 ng g −1 lipid. β-HBCD was detected in only one sample at 3.6 ng g −1 lipid while ∑ 4 PBDE ranged from 2.5 to 15.8 ng g −1 lipid. No temporal trend was apparent in HBCD concentrations in human milk collected in Australia from 1993 to 2009. In comparison, PBDE concentrations in human milk show a peak around 2002/03 (mean ∑ 4 PBDEs = 9.6 ng g −1 lipid) and 2003/04 (12.4 ng g −1 lipid) followed by a decrease in 2007/08 (2.7 ng g −1 lipid) and 2009 (2.6 ng g −1 lipid). In human blood serum samples collected from the Australian population, PBDE concentrations did not vary greatly ( p = 0.441) from 2002/03 to 2008/09. Continued monitoring including both human milk and serum for HBCD and PBDEs is required to observe trends in human body burden of HBCD and PBDEs body burden following changes to usage.

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction–liquid chromatography– electrospray–tandem mass spectrometry (on-line SPE–LC–ESI–MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L 1, respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L 1, were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.

The occurrence of 43 pharmaceuticals belonging to predominant therapeutic classes and their distribution in surface water, suspended solids and sediments has been investigated in the Ebro river basin in the Northeast of Spain. WWTP effluents were found to be a main source of contamination and the spatial distribution was affected by the river flow at the sampling point and corresponding dilution factor, resulting in higher concentrations and higher loads in small tributary rivers than in the Ebro river. The study showed that some compounds are preferentially found bound to suspended solids and not detected in river water. Generally, compounds with basic characteristics (pKa > 7) showed higher tendency to bind to suspended solids. The sediment samples generally presented lower concentrations than suspended solids.

This work describes the development, optimization and validation of an analytical method for the simultaneous detection and identification of 74 pharmaceutically active compounds (PhACs), from various therapeutic groups, in both environmental (ground and surface water) and wastewaters (WW). The method is based on the simultaneous extraction of all target compounds by solid phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by ultra high performance liquid chromatography (UHPLC) tandem mass spectrometry (MS/MS). Two selected reaction monitoring (SRM) transitions have been monitored per compound in order to fulfil the EC guidelines, as well as to ensure an accurate identification of target compounds in the samples. Quantification is performed by internal standard approach, applying 24 specific isotopically labeled compounds. The main advantages of the developed method, besides the selectivity and reliability of the results, is its high throughput. All compounds are extracted in a single step and the instrumental analysis lasts 5 min (NI mode)+8 min (PI mode), allowing fast throughput of samples. The limits of detection range from 0.01 to 50 ng L(-1), depending on the matrix, for most of the compounds. Finally, the method developed has been applied to the analysis of pharmaceuticals in the Ebro river basin (NE Spain).

Many substances related to human activities end up in wastewater and accumulate in sewage sludge. So far, there is only one extensive survey on the occurrence of UV filter residues in sewage sludge. However, more data are required to draw a reliable picture of the fate and effects of these compounds in the environment. This study attempts to fill this gap through the determination of selected UV filters and derivatives namely 4-methylbenzylidenecamphor, benzophenone-3, octocrylene, ethylhexylmethoxycinnamate, ethylhexyldimethyl PABA, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 4,4'-dihydroxybenzophenone in treated sewage sludge. The target compounds were extracted using pressurized liquid extraction and after this, determined by ultra high resolution liquid chromatography-tandem mass spectrometry. The determination was fast and sensitive, affording limits of detection lower than 19 ng g(-1) dry weight (dw) except for 2,4-dihydroxybenzophenone (60 ng g(-1) dw). Good recovery rates, especially given the high complexity of sludge matrix (between 70% and 102% except for 2,4-dihydroxybenzophenone (30%)) were achieved. The application of developed method allowed reporting for the first time the occurrence of two major degradation products of benzophenone-3 that have estrogenic activity in sewage sludge: 4,4'-dihydroxybenzophenone (in 5/15 WWTPs) and 4-hydroxybenzophenone (in 1/15 WWTPs). Results revealed the presence of UV filters in 15 wastewater treatment plants in Catalonia (Spain) at concentrations ranging from 0.04 to 9.17 μg g(-1) dw.

Estrogens constitute a recognized group of environmental emerging contaminants which have been proven to induce estrogenic effects in aquatic organisms exposed to them. Low removal efficiency in wastewater treatment plants results in the presence of this type of contaminants in surface waters and also even in finished drinking water. This manuscript reviews the environmental occurrence of natural (estrone, estradiol and estriol) and synthetic (ethynyl estradiol) estrogens in different water matrices (waste, surface, ground and drinking water), and their removal mainly via chemical oxidative processes. Oxidative treatments have been observed to be very efficient in eliminating estrogens present in water; however, disinfection by-products (DBPs) are generated during the process. Characterization of these DBPs is essential to assess the risk that drinking water may potentially pose to human health since these DBPs may also have endocrine disrupting properties. This manuscript reviews the DBPs generated during oxidative processes identified so far in the literature and the estrogenicity generated by the characterized DBPs and/or by the applied disinfection technology.

The artificial recharge of aquifers has become a valuable tool to increase water resources for drinking water production in many countries. In this work a total of 41 organic pollutants belonging to the classes of pesticides, estrogens, progestogens and volatile organic compounds (VOCs) have been monitored in the water from two artificial recharge plants located in Sweden and Denmark. The results from two sampling campaigns performed in each plant indicate good chemical status of the source water, as the contaminants detected were present at very low levels, far from those established in the legislation as maximum admissible concentrations (when existing) and far from those considered as a risk. Thus, of the 17 pesticides investigated, BAM (2,6-dichlorobenzamide), desethylatrazine, simazine, atrazine, terbuthylazine, diuron, metolachlor, and diazinon were the only compounds detected, and total pesticides levels were below 25 ng L−1, respectively. Estrone-3-sulfate was the only estrogen detected, at concentrations lower than 0.5 ng L−1. Progestogens were not found in any sample. Detected VOCs (benzene, toluene, ethylbenzene, and trichloroethylene) were below 0.04 μg L−1. The efficiency of elimination of these organic contaminants was poor as no significant decrease in their concentrations was observed through the recharge process., This work has been supported by the Energy, Environmental and Sustainable Development Program (Project ARTDEMO EVK1-CT2002-00114) and by the Spanish Ministry of Science and Innovation through the projects CEMAGUA (CGL2007-64551/HID) and SCARCE (Consolider-Ingenio 2010 CSD2009-00065). It reflects the author’s view. The EU is not liable for any use that may be made of the information contained in it. Merck (Darmstadt, Germany) is acknowledged for the gift of LC columns and off-line SPE cartridges.

In the present study the mechanisms of solar photodegradation of H2-receptor antagonist ranitidine (RNTD) were studied in a well-defined system of a pilot plant scale Compound Parabolic Collector (CPC) reactor. Two types of heterogeneous photocatalytic experiments were performed: catalysed by titanium-dioxide (TiO2) semiconductor and by Fenton reagent (Fe2+/H2O2), each one with distilled water and synthetic wastewater effluent matrix. Complete disappearance of the parent compounds and discreet mineralization were attained in all experiments. Furthermore, kinetic parameters, main intermediate products, release of heteroatoms and formation of carboxylic acids are discussed. The main intermediate products of photocatalytic degradation of RNTD have been structurally elucidated by tandem mass spectrometry (MS2) experiments performed at quadrupole-time of flight (QqToF) mass analyzer coupled to ultra-performance liquid chromatograph (UPLC). RNTD displayed high reactivity towards OH radicals, although a product of conduction band electrons reduction was also present in the experiment with TiO2. In the absence of standards, quantification of intermediates was not possible and only qualitative profiles of their evolution could be determined. The proposed TiO2 and photo-Fenton degradation routes of RNTD are reported for the first time., The study was financially supported by the EU Project INNOVA MED (INCO-CT-2006-517728) and the MICINN (Spain) “Programa de Acceso y Mejora de Grandes Instalaciones Científicas Españolas” (Plataforma Solar de Almería, GIC-05-17). Jelena Radjenovic gratefully acknowledges the JAE Program (Junta para la Ampliación de los Estudios), co-financed by CSIC (Consejo Superior de Investigaciones Científicas) and European Social Funds. Carla Sirtori wish to thank the CAPES foundation-Ministry of Education of Brazil for the Ph.D. Research Grant (BEX Processo: 3763-05-6).

A system of recirculating channels was used in this study to examine the long-term effects (29 d) of environmentally realistic concentrations of the herbicide diuron (from 0.07 to 7 μg L-1) on biofilm communities. The autotrophic activity of biofilms was affected by this herbicide, as reflected by a marked decrease in the photosynthetic efficiency. Diuron exposure also increased chlorophyll-a content and reduced the biovolume of diatom taxa at low concentrations. The effects on bacteria were also remarkable. Bacterial abundance was reduced after a week of exposure to the herbicide at a range of concentrations. Effects were on the number of live bacteria and on the increase in the leucine-aminopeptidase activity. It is suggested that inputs of herbicides to the river ecosystem at low concentrations may cause a chain of effects in the biofilm, which include inhibitory effects on algae but also indirect effects on the relationships between biofilm components. © 2009 Elsevier Ltd. All rights reserved This study was supported by the European Commission project Modelkey (Project 511237-2 GOCE). Additional funds were provided by the European Project Keybioeffects (MRTN-CT-2006-035695) and by the Spanish Ministry of Science and Technology (Project GCL2006-12785/HID) and the VIECO program (009/RN08/011) of the Spanish Ministry of the Environment and Rural and Marine Affairs

A sensitive magnetic particle enzyme-linked immunoassay (ELISA) was developed to analyze polybrominated diphenyl ethers (PBDEs) in water, milk, fish, and soil samples. The assay was rapid and can be used to analyze fifty samples in about 1h after sample cleanup. The assay has a limit of detection (LOD) below 0.1 ppb towards the following brominated diphenyl ether (BDE) congeners: BDE-47, BDE-99, BDE-28, BDE-100, and BDE-153, with the LOD approximately the same as GC-NCI-MS. The congeners most readily recognized in the ELISA were BDE-47 and BDE-99 with the cross-reactivities of BDE-28, BDE-100, and BDE-153 being less than 15% relative to BDE-47. As anticipated, the sensitivities are proportional to the similarities between the hapten structure and the BDE congener structure. Some oxygenated congeners with structural similarity to the hapten showed high to moderate cross-reactivities. Very low cross-reactivity was observed for other PBDEs or chlorinated environmental contaminants. The assay gave good recoveries of PBDEs from spiked water samples and a very small within and between day variance. Comparison with GC-NCI-MS demonstrated the ELISA method showed equivalent precision and sensitivity, with better recovery. The lower recovery of the GC-NCI-MS method could be caused by the use of an internal standard other than an isotopically substituted material that could not be used because of the fragmentation pattern observed by this method. The cleanup methods prior to ELISA were matrix dependent, no pretreatment was needed for environmental water samples, while fish, milk, and soil samples required various degrees of cleanup. Analysis of this wide variety of environmental samples by both ELISA and GC-MS demonstrated ELISA provides a timely and cost-effective method to screen for PBDEs in a variety of samples.

Population growth and unpredictable climate changes will pose high demands on water resources in the future. Even at present, surface water is certainly not enough to cope with the water requirement for agricultural, industrial, recreational and drinking purposes. In this context, the usage of ground water has become essential, therefore, their quality and quantity has to be carefully managed. Regarding quantity, artificial recharge can guarantee a sustainable level of ground water, whilst the strict quality control of the waters intended for recharge will minimize contamination of both the ground water and aquifer area. However, all water resources in the planet are threatened by multiple sources of contamination coming from the extended use of chemicals worldwide. In this respect, the environmental occurrence of organic micropollutants such as pesticides, pharmaceuticals, industrial chemicals and their metabolites has experienced fast growing interest. In this paper an overview of the priority and emerging organic micropollutants in the different source waters used for artificial aquifer recharge purposes and in the recovered water is presented. Besides, some considerations regarding fate and removal of such compounds are also addressed.

The aim of this investigation was to evaluate the environmental impact associated to PCDDs/Fs and dioxin-like PCBs in the Ebro River basin. Sediments and fish from several species were sampled at three sites with different historical pollution records, including the Barbastro area with different industrial activities, and the Flix and Monzón sites, associated to heavy organochlorine compound pollution. Seventeen toxic PCDDs/Fs and 12 dioxin-like PCBs were analyzed by GC-MS. The results obtained indicated significant accumulation of dioxin-like PCBs, but not PCDDs/Fs, in sediments and fish at the Flix site compared to the other sites. Concomitantly, cytochrome p450 1A (CYP1A) expression, a known indicator for pollution by dioxins and dioxin-like PCBs, was significantly elevated in barbel (Barbus graellsii) from the Flix site, compared to the population from the Barbastro site. CYP1A expression correlated with the concentration of dioxin-like PCBs in the fish fat, whereas no significant correlation was found with PCDDs/Fs concentrations. Our data suggest a significant biological impact at the Flix site, closely related to the presence of dioxin-like PCBs, whereas the PCDDs/Fs contribution to this impact appears to be non-significant, at least in the studied sites.

The Cinca River is a tributary of Ebro River in the NE of Spain which receives input from different activities. One of the most important is related to an industry where DDT is used as an intermediate in the production of dicofol. This study evaluated the DDT contamination along the Cinca River. Sampling sites were selected up- and downstream from this industry. Sediments and fishes (59 bleaks (Alburnus alburnus) and 23 barbels (Barbus graellsi)) were collected in 2002 and analyzed using a new and rapid selective pressurized liquid extraction (SPLE) method. DDT and its metabolites were found in sediments and fishes at levels ranging from 9 to 94microg kg(-1) dry weight (d.w.) and from not detected to 2098microg kg(-1) wet weight (w.w.), respectively. The highest values corresponded to samples collected just downstream the industry. Thirty kilometers downstream from the factory, levels were clearly lower, showing a weakening of the impact. p,p'-DDE isomer comprised up to 50% and 70% of total DDT measured in sediment and fish, respectively. When compared with values obtained in a previous study in 1999, a generalized drop of the levels in all matrixes (77-97%), was observed. No meaningful differences were found between the two fish species studied neither between the two tissues (muscle and liver) analyzed.

Several halogenated flame retardants were detected in black kite, white stork and greater flamingo unborn eggs from Donana Natural Space (Spain) collected in 1999, 2003, 2011 and 2013. The main components of Penta-BDE commercial mixture (BDE-47, -99 and -100) showed a decrease in the studied time interval, concurring with the ban of this mixture in the European Union (EU) in 2006. On the other hand, BDE-209, the main component of Deca-BDE mixture showed a clear trend in black kites but further monitoring is needed since its production ceased at the end of 2013. Besides, even if Dechlorane Plus (DP) was proposed by the EU as an alternative to BDE-209 no time trends were observed. Furthermore, total concentrations of PBDEs (classical FRs) are still higher than concentrations of hexabromocyclododecane (HBCD) and alternative FRs halogenated norbornenes (HNs), which are theoretically substitutes of the already banned PBDEs.

This study describes the biotransformation of cytostatic and immunosuppressive pharmaceutical methotrexate. Its susceptibility to microbiological breakdown was studied in a batch biotransformation system, in presence or absence of carbon source and at two activated sludge concentrations. The primary focus of the present study are methotrexate biotransformation products, which were tentatively identified by the ultra-high performance liquid chromatography-quadrupole - Orbitrap-MS. Data-dependent experiments, combining full-scan MS data with product ion spectra were acquired, in order to identify the molecular ions of methotrexate transformation products, to propose the molecular formulae and to elucidate their chemical structures. Among the identified transformation products 2,4-diamino-N10-methyl-pteroic acid is most abundant and persistent. Other biotransformation reactions involve demethylation, oxidative cleavage of amine, cleavage of C-N bond, aldehyde to carboxylate transformation and hydroxylation. Finally, a breakdown pathway is proposed, which shows that most of methotrexate breakdown products retain the diaminopteridine structural segment. In total we propose nine transformation products, among them eight are described as methotrexate transformation products for the first time., a Jožef Stefan Institute, Department of Environmental Sciences, Jamova 39, Ljubljana, Slovenia b Water and Soil Quality Research Group, Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), Jordi Girona 18-26, Barcelona, Spain c Catalan Institute for Water Research (ICRA), Scientific and Technological Park of the University of Girona, H2O Building Emili Grahit 101, Girona, Spain

The present study describes the development, validation and application of a fully automated analytical method based on on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry (on line SPE-HPLC-MS/MS) to assess the removal efficiency in water works and the ecotoxicological implications derived of the two most used benzotriazole-class UV stabilizers (BZTs), namely 1H-benzotriazole (BZT) and 5-methyl-1H-benzotriazole (MeBZT). Influent and effluent wastewater samples from 20 wastewater treatment plants (WWTPs) were analyzed. Removal rates (RE%) and half-lives (t1/2) for each BZTs were calculated and correlated to the hydraulic retention time (HRT) of each plant. Both BZTs were detected in all influent and effluent samples (concentrations in the range 26.7 ng L(-1)-42.9 μg L(-1)), with the highest concentrations corresponding to MeBZT. Results indicated that both compounds were recalcitrant (RE% in the range 11.8-94.7%) and that no clear influence of HRT on removals could be drawn. Finally, the potential environmental risk posed by the levels of BZTs detected was evaluated calculating the hazard quotients (HQs) MeBZT was the only BZTs posing a risk to Vibrio fischeri, Daphnia galeata and Pimephales promelas.

Polychlorinated biphenyls, dibenzodioxins and dibenzofurans were analysed in eggs of a protected gull species, the Audouin's Gull (Larus audouinii) and compared to those of the Yellow-legged Gull (Larus cachinnans), both breeding in the Western Mediterranean (Ebro Delta and Medes Islands, respectively). Differences in concentrations as well as in congener profiles reflected differences in both habitat and diet of the two species. Levels of AHH-active PCB congeners were lower in Yellow-legged Gull (0.4-1.6 micrograms/g d.w) than in Audouin's Gull eggs (1.2-33.9 micrograms/g d.w.). These concentrations, expressed in international toxic equivalence factors (i-TEQ/g d.w.), were on average 24 times higher in the Audouin's gull. I-TEQ levels due to dioxins were also higher in this species by a factor of ca. 7. I-TEQ levels related to PCBs resulted 90-230 times higher than those of dioxins and furans. Thus, AHH-inducing PCBs might represent even higher toxicological hazards than dioxins and furans to some populations of seabirds. The necessity of assessing the impact of these compounds in rare and protected species is pointed out.

The aim of this study was to test if pharmaceuticals could explain observed responses of field collected and transplanted invertebrate species (Hydropsyche exocellata, Echinogammarus longisetosus, and Daphnia magna). The study was performed in the middle and lower course of Llobregat river basin, which is affected by pharmaceuticals and other pollutants coming from sewage treated effluents. Up to 10 different endpoints including enzyme activities related with detoxication mechanisms (i.e. glutathione S transferase, catalase, esterases), the oxidative stress damage marker (lipid peroxidation), and individual responses (mortality, post-exposure feeding rates) were assessed. Biological responses were complemented with a detailed chemical analysis of metals, detergents, pesticides, pharmaceuticals and other general water quality variables to allow identifying causal abiotic factors. Estimated hazard indexes of measured pollutants indicated that pesticides and metals accounted for most of the predicted toxicity (>95%) in the most contaminated site and that the predicted toxicity of pharmaceuticals was marginal (

This article describes the photolysis of azithromycin, a macrolide antibiotic with reported occurrence in environmental waters, under simulated solar radiation. The photodegradation followed first-order reaction kinetics in five matrices examined. In HPLC water, the degradation rate was the slowest (half-life: 20 h), whereas in artificial freshwater supplemented with nitrate (5 mg L−1) or humic acids (0.5 mg L−1) the degradation of azithromycin was enhanced by factors of 5 and 16, respectively, which indicated the role of indirect photolysis involving the formation of highly reactive species. Following chromatographic separation on a UPLC system, the characterization of the transformation products was accomplished using high-resolution QqToF-MS analysis. The presence of seven photoproducts was observed and their formation was postulated to originate from (bis)-N-demethylation in the desosamine sugar, O-demethylation in the cladinose sugar, combinations thereof, as well as from hydrolytic cleavages of the desosamine and/or cladinose residue. Two of these photoproducts could also be detected in natural photodegradation process in river water which was spiked with azithromycin.