Search

Wastewater Treatment Plants (WWTPs) generate a substantial amount of sludge as a residue of the wastewater treatment process. The management of this sludge requires the adoption of cost-effective and environmentally friendly techniques. Sludge Treatment Wetlands (STW) have emerged as an effective means to manage and treat sludge, resulting in the production of biosolids suitable for agricultural purposes. This study aimed to ascertain the optimal operation in terms of final rest period for STWs in the Mediterranean region to boost the production of biosolids for agricultural applications. Two WWTPs in Spain were monitored for a period of 9 months, during which several physic-chemical parameters were monitored to determine the optimal final rest period. The findings revealed that, when sludge feeding period was stopped in summer, a final rest period of 6 months was sufficient to reach biosolids suitable for agricultural re-use. These biosolids displayed a content of 53% total solids (TS), a mineralization rate of 40% volatile solids (VS/TS), a stabilization degree (SD) of 40%, and a high nutrient content. Moreover, the presence of heavy metals, pathogens, antimicrobial resistance genes (ARGs), antibiotics, and pesticides was generally low. Overall, this study demonstrates that, in the Mediterranean Region, 6 months of rest period starting in summer are appropriate for sludge treatment wetlands to effectively generate biosolids with suitable characteristics to be safely re-used as a bio-based fertilizer., 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.)

Chemical pollution is still an underestimated threat to surface waters from natural areas. This study has analysed the presence and distribution of 59 organic micropollutants (OMPs) including pharmaceuticals, lifestyle compounds, pesticides, organophosphate esters (OPEs), benzophenone and perfluoroalkyl substances (PFASs) in 411 water samples from 140 Important Bird and Biodiversity Areas (IBAs) from Spain, to evaluate the impact of these pollutants in sites of environmental relevance. Lifestyle compounds, pharmaceuticals and OPEs were the most ubiquitous chemical families, while pesticides and PFASs showed a detection frequency below 25% of the samples. The mean concentrations detected ranged from 0.1 to 301 ng/L. According to spatial data, agricultural surface has been identified as the most important source of all OMPs in natural areas. Lifestyle compounds and PFASs have been related to the presence of artificial surface and wastewater treatment plants (WWTPs) discharges, which were also an important source of pharmaceuticals to surface waters. Fifteen out of 59 OMPs have been found at levels posing a high risk for the aquatic IBAs ecosystems, being the insecticide chlorpyrifos, the antidepressant venlafaxine and perfluorooctanesulfonic acid (PFOS) the most concerning compounds. This is the first study to quantify water pollution in IBAs and evidence that OMPs are an emerging threat to freshwater ecosystems that are essential for biodiversity conservation., 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 The Authors. Published by Elsevier B.V. All rights reserved.)

Flame retardants (FRs) are widely used in consumer products including furniture foam and electronic equipment such as computers, monitors and TVs. Over time, FRs can easily migrate into the surrounding environments. Since brominated FRs (BFRs) has been determined of high concern due to their environmental persistence, bioaccumulation and potential toxicity, novel FRs have emerged. The present study was aimed at identifying and quantifying the indoor levels of 41 legacy and novel FRs, which include 20 OPFRs and 21 HFRs (8 PBDEs, 3 HBCDDs, 5 NBFRs and 5 DECs) in Tarragona Province (Catalonia, Spain). The results have confirmed the presence of both legacy and novel FRs in air and dust of homes, schools and offices. To the best of our knowledge, this is the first European study measuring OPFRs at office environments and also confirming the presence of the following OPFRs: TEP, TCIPP, T2IPPP, TPPO, DCP, TMCP and B4IPPPP in indoor air, even some of them at high levels. OPFRs in general and TCIPP in particular showed high concentrations in air (94,599 pg/m 3 and 72,281 pg/m 3 , respectively) and dust (32,084 ng/g and 13,496 ng/g, respectively) samples collected in indoor environments. HBCDDs were found at high levels in dust (32,185 ng/g), whereas the presence of PBDEs and DECs were low in both matrices (<160 pg/m 3 in air and <832 ng/g in dust). NBFRs showed higher levels than the two legacy FRs groups, which is supported by the current restrictions of these FRs (640 pg/m 3 in air and 1291 ng/g in dust). Samples of schools had significantly lower levels of NBFRs, but significantly higher concentrations of HFRs in air than in home samples, while dust levels of HFRs were significantly lower than those in samples of offices. Regarding human health risks, the current assessment suggests that those derived from exposure to FRs were lower -although close- to assumable risks, evidencing the potential of FRs for non-carcinogenic and carcinogenic risks, mainly due to the exposure to TCIPP, which was the main contributor together with ΣHBCDDs and also EHDPP., 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 © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Nowadays, the presence of microplastics in drinking water is of concern worldwide due to potential impacts on human health. This paper has examined the presence of microplastics along the Llobregat river basin (Catalonia, Spain) and studied their behaviour and elimination along the drinking water treatment plant (DWTP). Due to different water composition, different sampling and sample preparation protocols were used to determine microplastics from river water and in the DWTP. Identification of microplastics of size range from 20 μm to 5 mm was performed by fourier-transform infrared spectroscopy (FTIR). Microplastics were detected in 5 out of 7 points along the Llobregat basin, with concentrations ranging between non-detected and 3.60 microplastics/L. In the intake of the DWTP, the mean concentration was 0.96 ± 0.46 microplastics/L (n=5), with a predominance of polyester (PES) and polypropylene (PP) and at the outlet the mean concentration was of 0.06 ± 0.04 microplastics/L with an overall removal efficiency of 93 ± 5%. Sand filtration was identified as the key stage in microplastic removal (78 ± 9%). Furthermore, the results showed that ultrafiltration/reverse osmosis (advanced treatment) is more effective for microplastic removal than ozonation/carbon filtration stage (upgraded conventional treatment). In addition, a preliminary migration test of the different materials used in the DWTP has been performed to identify potential sources of microplastics in each treatment step., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Senior residences are health-care facilities that are socially-accepted for the assistance of elderly people. Since the elderly account for the foremost pharmaceutical-consuming age-group, senior residences become a hot-spot for pharmaceuticals discharge to the sewage grid. The objectives of the present study were to identify the bioactive pharmaceuticals in sewage waters from senior residences and to propose an on-site monitoring strategy for their control. In this study, we have studied the presence of 43 pharmaceuticals highly consumed by the elderly population in six senior residences located in Spain, France and Portugal. Wastewater was sampled directly from the water-chest in each residence during different times of the day throughout one week. Main compounds detected at the high µg L -1 level were analgesic and antipyretic drugs such as acetylsalicylic acid, paracetamol, ibuprofen; antibiotics such as amoxicillin and sulfamethoxazole; compounds for the treatment of neuropathies as gabapentin, trazodone and valsartan; pharmaceuticals for the treatment of diabetes (vildagliptin) and anticancer drugs. The daily loads discharged were estimated and their fate was evaluated. The final objective of this study is to highlight the need to implement at-source waste water treatment procedures in senior residences, which have been identified as a point source pollution of pharmaceuticals.

The air humidity in Antarctica is very low and this peculiar weather parameter make the use of flame retardants in research facilities highly needed for safety reasons, as fires are a major risk. Legacy and novel flame retardants (nFRs) including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), Dechlorane Plus (DP), and other nFRs were measured in indoor dust samples collected at research Stations in Antarctica: Gabriel de Castilla, Spain (GCS), Julio Escudero, Chile (JES), and onboard the RRS James Clark Ross, United Kingdom (RRS JCR). The GC-HRMS and LC-MS-MS analyses of dust samples revealed ∑ 7 PBDEs of 41.5 ± 43.8 ng/g in rooms at GCS, 18.7 ± 11.6 ng/g at JES, and 27.2 ± 37.9 ng/g onboard the RRS JCR. PBDE pattern was different between the sites and most abundant congeners were BDE-183 (40%) at GCS, BDE-99 (50%) at JES, and BDE-153 (37%) onboard the RRS JCR. The ∑ (4) HBCDs were 257 ± 407 ng/g, 14.9 ± 14.5 ng/g, and 761 ± 1043 ng/g in indoor dust collected in rooms at GCS, JES, and RRS JCR, respectively. The ∑ 9 nFRs were 224 ± 178 ng/g at GCS, 14.1 ± 13.8 ng/g at JES, and 194 ± 392 ng/g on the RRS JCR. Syn- and anti-DP were detected in most of the samples and both isomers showed the highest concentrations at GCS: 163 ± 93.6 and 48.5 ± 61.1 ng/g, respectively. The laboratory and living room showed the highest concentration of HBCDs, DPs, BTBPE. The wide variations in FR levels in dust from the three research facilities and between differently used rooms reflect the different origin of furnishing, building materials and equipment. The potential health risk associated to a daily exposure via dust ingestion was assessed for selected FRs: BDEs 47, 99, and 153, α-, β-, and γ-HBCD, BTBPE, syn- and anti-DP. Although the estimated exposures are below the available reference doses, caution is needed given the expected increasing use of novel chemicals without a comprehensive toxicological profile., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Two different methodologies were combined to evaluate the risks that antibiotics can pose in the environment; i) an effect-based methodology based on microbial growth inhibition and ii) an analytical method based on liquid-chromatography coupled to mass spectrometry (LC-MS). The first approach was adapted and validated for the screening of four antibiotic families, specifically macrolides/β-lactams, quinolones, sulfonamides and tetracyclines. The LC-MS method was applied for the identification and quantification of target antibiotics; then, the obtained results were combined with ecotoxicological data from literature to determine the environmental risk. The two methodologies were used for the analysis of antibiotics in water samples (wastewater, river water and seawater) and biofluids (fish plasma and mollusk hemolymph) in two monitoring campaigns undertaken in the Ebro Delta and Mar Menor Lagoon (both in the Mediterranean coast of Spain). Both approaches highlighted macrolides (azithromycin) and quinolones (ciprofloxacin and ofloxacin) as the main antibiotics in wastewater treatment plant (WWTP) effluents with potential risk for the environment. However, no risk for the aquatic life was identified in the river, lagoon and seawater as antibiotic levels were much lower than those in WWTP effluents. Fish from Ebro River were the organisms presenting the highest antibiotic concentration when compared with bivalves (mussels) from the Mediterranean Sea and gastropods (marine snails) from the Mar Menor Lagoon. The effect-based methodology successfully determined antibiotic risk in wastewater, but its applicability was less clear in environmental waters such as seawater, due to its high detection limits. Improving sample preconcentration could increase the method sensibility. Overall, combination of both methodologies provides comprehensive insights in antibiotic occurrence and risk associated in areas under study., 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.)

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 (EC 50 ) decreased with increasing octanol-water partition coefficients. The EC 50 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., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Besides anthropogenic contamination, freshwater environments can also be affected by the presence of natural toxins. Mycotoxins, plant toxins and cyanotoxins are the most relevant groups that can be found in the aquatic system. However, until now, only cyanotoxins have been more carefully studied. In the present work, single workflow for the assessment of natural toxins in waters, based on suspect screening and target screening of a selected group of toxins is presented. The approach is based on a triple-stage solid-phase extraction (SPE) able to isolate a wide range of natural toxins of different polarities, followed by liquid chromatography coupled to high-resolution mass spectrometry (HPLC-ddHRMS 2 ) using a Q-Exactive Orbitrap analyser. The acquisition was performed in full-scan (FS) and data-dependant acquisition (ddMS 2 ) mode, working under positive and negative mode. For the tentative identification, different on-line databases such as ChemSpider and MzCloud and an in-house natural toxins list with 2384 structures, that includes cyanotoxins, plant toxins and mycotoxins, were used. Also, thanks to the MS 2 data, it was possible to achieve a high level of tentative identification confidence, but confirmation was only possible comparing the standards of the suspected compounds. For those, the analytical parameters of the developed method were also validated, and the quantification was possible by external calibration. Validation showed recoveries in the range between 53 and 95%, and method limits of detection (MDL) between 0.02 and 1.22 μg/L. This approach was applied to study natural toxins in 4 sampling sites along the Ter River in Catalonia (NE Spain). In this preliminary study 23 natural toxins were tentatively identified, and 9 of them confirmed (aflatoxin B1, anatoxin-a, nodularin, microcystin-LR, baicalein, kojic acid, cinchonine, B-asarone and atropine). The results of the quantification of these compounds showed concentrations below 1 μg/L in all cases, that is considered safe according to the actual legislation. This suspect screening approach allows a more comprehensive assessment of natural toxins in natural waters., 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 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

This study presents the application of a suspect screening approach to screen a wide range of natural toxins, including mycotoxins, bacterial toxins, and plant toxins, in surface waters. The method is based on a generic solid-phase extraction procedure, using three sorbent phases in two cartridges that are connected in series, hence covering a wide range of polarities, followed by liquid chromatography coupled to high-resolution mass spectrometry. The acquisition was performed in the full-scan and data-dependent modes while working under positive and negative ionisation conditions. This method was applied in order to assess the natural toxins in the Ter River water reservoirs, which are used to produce drinking water for Barcelona city (Spain). The study was carried out during a period of seven months, covering the expected prior, during, and post-peak blooming periods of the natural toxins. Fifty-three (53) compounds were tentatively identified, and nine of these were confirmed and quantified. Phytotoxins were identified as the most frequent group of natural toxins in the water, particularly the alkaloids group. Finally, the toxins identified to levels 2 and 1 were prioritised according to their bioaccumulation factor, biodegradability, frequency of detection, and toxicity. This screening and prioritisation approach resulted in different natural toxins that should be further assessed for their ecotoxicological effects and considered in future studies.

A comprehensive monitoring of a broad set of antibiotics in the final effluent of wastewater treatment plants (WWTPs) of 7 European countries (Portugal, Spain, Ireland, Cyprus, Germany, Finland, and Norway) was carried out in two consecutive years (2015 and 2016). This is the first study of this kind performed at an international level. Within the 53 antibiotics monitored 17 were detected at least once in the final effluent of the WWTPs, i.e.: ciprofloxacin, ofloxacin, enrofloxacin, orbifloxacin, azithromycin, clarithromycin, sulfapyridine, sulfamethoxazole, trimethoprim, nalidixic acid, pipemidic acid, oxolinic acid, cefalexin, clindamycin, metronidazole, ampicillin, and tetracycline. The countries exhibiting the highest effluent average concentrations of antibiotics were Ireland and the southern countries Portugal and Spain, whereas the northern countries (Norway, Finland and Germany) and Cyprus exhibited lower total concentration. The antibiotic occurrence data in the final effluents were used for the assessment of their impact on the aquatic environment. Both, environmental predicted no effect concentration (PNEC-ENVs) and the PNECs based on minimal inhibitory concentrations (PNEC-MICs) were considered for the evaluation of the impact on microbial communities in aquatic systems and on the evolution of antibiotic resistance, respectively. Based on this analysis, three compounds, ciprofloxacin, azithromycin and cefalexin are proposed as markers of antibiotic pollution, as they could occasionally pose a risk to the environment. Integrated studies like this are crucial to map the impact of antibiotic pollution and to provide the basis for designing water quality and environmental risk in regular water monitoring programs., 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

One of the major challenges currently faced is to develop systematic ways of addressing chemical mixtures in environmental assessment. With this purpose, a simple, rapid, and sensitive method for the detection and quantification of a mixture of relevant contaminants in molluscs has been developed. The method is based on QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and Ultra-High Performance Liquid Chromatography-High Resolution Mass Spectrometry (UHPLC-HRMS). It includes a mixture of 23 compounds formed by pesticides, endocrine disruptors and pharmaceuticals (metolachlor, simazine, desethylatrazine, atrazine, thiabendazole, diazinon, malathion, bentazone, MCPA, propanil, acetamiprid, imidacloprid, caffeine, bisphenol A, triclosan, triclocarban, methylparaben, ethylparaben, propylparaben, 1H-benzotriazole, sulfamethoxazole, venlafaxine and carbamazepine). The method was developed and validated in 4 different types of shellfish of high commercial interest such as mussel (Mytilus galloprovincialis), oyster (Crassostrea gigas), cockle (Cerastoderma edule) and razor shell (Solen marginatus). The mean percentage of recoveries obtained for all the compounds in each mollusc type (intra-specie) ranged from 96% to 107% showing the good performance of the method developed. The relative standard deviation was under 10% for the intra-day and 17% inter-day analyses. Method detection limits and method quantification limits were below 10 ng/g dry weight for all the species and compounds targeted. Finally, the method was applied to aquaculture samples, oysters and cockles, from Ebro Delta (Spain), after some episodes of mortality occurred in 2017. A high level of bisphenol A was detected in C. edule which may explain the mortality suffered by this organism. C. gigas presented low levels of metolachlor, bentazone, acetamiprid, and methylparaben., (Copyright © 2019. Published by Elsevier B.V.)

Despite the social concern about the generalization of antibiotic resistance hotspots worldwide, very little is known about the contribution of different potential sources to the global risk. Here we present a quantitative analysis of the distribution of Antibiotic Resistance Genes (ARGs) in soil, rhizospheric soil, roots, leaves and beans in tomato, lettuce and broad beans crops (165 samples in total), grown in nine commercial plots distributed in four geographical zones in the vicinity of Barcelona (North East Spain). We also analyzed five soil samples from a nearby forest, with no record of agricultural activities. DNA samples were analyzed for their content in the ARGs sul1, tetM, qnrS1, bla CTX-M-32 , bla OXA-58 , mecA, and bla TEM , plus the integron intI1, using qPCR methods. In addition, soil microbiomes from the different plots were analyzed by amplicon-targeted 16S rRNA gene sequencing. Our data show a decreasing gradient of ARG loads from soil to fruits and beans, the latter showing only from 0.1 to 0.01% of the abundance values in soil. The type of crop was the main determinant for both ARG distribution and microbiome composition among the different plots, with minor contributions of geographic location and irrigation water source. We propose that soil amendment and/or fertilization, more than irrigation water, are the main drivers of ARG loads on the edible parts of the crop, and that they should therefore be specifically controlled., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Organic pollutants are continuously being introduced in seawater with uncharacterized impacts on the engines of the marine biogeochemical cycles, the microorganisms. The effects on marine microbial communities were assessed for perfluoroalkyl substances, organophosphate esters flame retardants and plasticizers, polycyclic aromatic hydrocarbons, and n-alkanes. Dose-response experiments were performed at three stations and at three depths in the NW Mediterranean with contrasted nutrient and pollutant concentrations. In these experiments, the microbial growth rates, the abundances of the main bacterial groups, measured by Catalyzed Reporter Deposition Fluorescence In Situ Hybridization (CARD-FISH), and extracellular enzymatic activities, were quantified. Increasing concentrations of organic pollutants (OPs) promoted different responses in the communities that were compound, organism and nutrient availability (trophic status). The largest differences between OP treatments and controls in the growth rates of both heterotrophic and phototrophic microbial groups were observed in seawater from the deep chlorophyll maxima. Furthermore, there was a compound specific stimulation of different extracellular enzymatic activities after the exposure to OPs. Our results revealed that marine microbial communities reacted not only to hydrocarbons, known to be used as a carbon source, but also to low concentrations of organic pollutants of emerging concern in a complex manner, reflecting the variability of various environmental variables. Multiple linear regressions suggested that organic pollutants modulated the bacterial growth and extracellular enzymatic activities, but this modulation was of lower magnitude than the observed pronounced response of the microbial community to nutrient availability., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The main objective of the present study is to prioritize those pharmaceuticals that have higher chances to be detected in water due to incomplete removal in Wastewater Treatment Plants (WWTPs). To do so, the total consumption of pharmaceuticals in Catalonia (NE Spain) were compiled to calculate the predicted environmental concentrations (PECs) in wastewater effluents and in river water. PECs were estimated using publicly available consumption data in the period of 2013-2016 for a suite of 165 compounds. The selected compounds were based on generic pharmaceuticals with emphasis on drugs consumed by people aged 65 or over as they represent the age group with the highest consumption of pharmaceuticals. The mean total consumption of pharmaceuticals in the period studied was of 623 ± 3 t per year. Paracetamol, metformin and ibuprofen were the most administered drugs although the highest PEC values corresponded to metformin, amoxicillin and metamizole. Finally, predicted environmental levels together with acute and chronic toxicological data allowed estimating the risks of these compounds. Amoxicillin is expected to pose adverse effects for cyanobacteria, whereas metformin and ibuprofen pose a small potential for adverse effects to invertebrates and fish, respectively., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This study evaluated the occurrence and distribution of 81 pharmaceutically active compounds (PhACs) in the vulnerable area of the Ebro Delta region (Catalonia, Spain), to assess the environmental impact of wastewater treatment plants discharge to coastal environments. The occurrence of PhACs was followed along the wastewater-recipient water-sediment chain until they reach estuaries and the Mediterranean Sea. Water and sediment samples were collected in an integrated way at different sampling points covering three different seasons in reaches of the Ebro River located upstream and downstream from wastewater treatment plants (WWTPs), surrounding channels, estuaries, and the associated receiving seawater. 28 out of the 57 compounds detected in effluent wastewater were positively identified in estuary and seawaters, revealing that WWTP discharges are an important source of contamination in coastal environments and that PhACs are suitable markers of urban contamination in these areas. The substances with the highest frequency of detection belonged to the groups of analgesics/anti-inflammatories (acetaminophen, salicylic acid), antihypertensives (valsartan), psychiatric drugs (carbamazepine), and antibiotics (clarithromycin, trimethoprim). In general, a decrease in concentration was observed from inland sampling points towards the Mediterranean Sea, resulting from a dilution in the recipient marine water bodies. A reduced number of PhACs, at concentrations ranging from 0.1 to 12.5 ng g -1 dry weight (d.w.) was detected in sediment samples, indicating that sorption is a minor natural attenuation pathway for these compounds. Finally, a prioritization strategy, based on the compounds concentration and frequency of detection in seawater, removal efficiency in WWTP, bioaccumulation potential, toxicity to marine organisms and persistency, was used to highlight the PhACs of major ecological concern and that could be used as relevant indicators of wastewater contamination in coastal environments., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The longitudinal structure of the environmental and phytoplankton variables was investigated in the Ebro River (NE Spain), which is heavily affected by water abstraction and regulation. A first exploration indicated that the phytoplankton community did not resist the impact of reservoirs and barely recovered downstream of them. The spatial analysis showed that the responses of the phytoplankton and environmental variables were not uniform. The two set of variables revealed spatial variability discontinuities and river fragmentation upstream and downstream from the reservoirs. Reservoirs caused the replacement of spatially heterogeneous habitats by homogeneous spatially distributed water bodies, these new environmental conditions downstream benefiting the opportunist and cosmopolitan algal taxa. The application of a spatial auto-regression model to algal biomass (chlorophyll-a) permitted to capture the relevance and contribution of extra-local influences in the river ecosystem., (Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.)

Determining the exposure and magnitude at which various pollutants are differentially assimilated at the breeding and non-breeding grounds of migratory wildlife is challenging. Here, the possibility of applying the migratory connectivity framework to understanding contamination in birds is illustrated by considering flame retardants in inviable eggs of a migratory raptor, the black kite (Milvus migrans). The occurrence and concentration of legacy and emerging compounds in eggs from the southeastern peri-urban area of Madrid city, central Spain, were compared with those from Doñana National Park in southern Spain. A much higher occurrence and concentration of multiple polybrominated diphenyl ethers and Dechlorane 602 were found in Madrid than Doñana, but the opposite patterns were found for Dechlorane Plus. Individuals from these and other breeding areas in western Europe showed a strong intermixing pattern over widespread wintering areas in Africa, as assessed by ringing recoveries and movements tracked by satellite devices. This diffuse migratory connectivity reveals breeding areas as the main contamination grounds. High contamination burdens sequestered in eggs point to rapid assimilation of these compounds before laying, associated with important emission sources in Madrid, especially landfills of partially incinerated urban refuse, and other anthropogenic operations. Diet composition regarding aquatic vs. terrestrial prey, and bioaccumulation and biomagnification processes are suggested to explain differential assimilation of some compounds, especially Dechlorane Plus in Doñana, although a local emission source polluting this area cannot be ruled out. Insight from the migratory connectivity framework can help to disentangle large-scale patterns of contaminant uptake and refocus attention on key regions and potential causes of chemical hazards in declining migratory species and human populations., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The presence, sources and partitioning of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylate, C4, C6-C10 sulfonates and C8 sulfonamide) were assessed in water, sediment, and biota of the Jucar River basin (E Spain). Considering the three matrices, perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (PFOS) were the most frequent compounds, being remarkable the high occurrence of short-chain PFASs (C≤8), which are intended to replace the long-chain ones in several industrial and commercial applications. In general, all samples were contaminated with at least one PFAS, with the exception of three fish samples. Mean concentrations detected in sediments (0.22-11.5ng g(-1)) and biota (0.63-274µgkg(-1)) samples were higher than those measured in water (0.04-83.1ngL(-1)), which might suggest (bio) accumulation. The occurrence of PFAS is related to urban and industrial discharges (Cuenca city in the upper part of basin, and car's factory, and effluents of the sewage treatment plant (STP) of Alzira, in the lower part). Increasing pollution gradients were found. On the other hand, higher contamination levels were observed after regulation dams of the catchment pointing out their importance in the re-distribution of these contaminants. None of the hazard quotients (HQ) calculated indicate potential risk for the different tropic levels considered (algae, Daphnia sp. and fish). PFAS concentrations found in this study can be considered in acceptable levels if compared to existing Regulatory Legislation and, consequently, they do not pose an immediate human health risk., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The aim of this study was to evaluate the presence and distribution of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and biphenyls (PCBs), concretely those so-called as dioxin-like PCBs, in yellow-legged gull eggs (Larus michahellis) collected from five Natural Parks (some of them National Parks) in Spain during the period 2010-2013. PCDD/Fs and dl-PCBs were detected in all the samples. Due to the proximity to important urban and industrial areas higher concentrations were determined in colonies located in the Northern Mediterranean coast than those found in the Southern Mediterranean or Atlantic colonies where a softer anthropogenic impact occurs. Mean ∑PCDD/F concentrations ranged from 49 to 223pg/g lipid weight (lw) and ∑dl-PCB concentrations varied from 146 to 911ng/g lw. In the Natural Park of the Ebro Delta (Northern Mediterranean coast) two gull species share habitat: yellow-legged and Audouin gull (Larus audouinii). Eggs from both species were collected and PCDD/F and dl-PCB levels compared. The species that feeds exclusively on pelagic fish (L. audouinii) had significantly higher PCDD/F and dl-PCB levels than the scavenger L. michahellis, pointing out the diet-dependent differences in the accumulation of persistent organic pollutants between similar cohabitant breeding species. Finally, mean TEQ values were in general below those considered as critical for toxicological effects in birds., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The bioaccumulation of 20 pharmaceuticals in cockle (Cerastodema glaucum), noble pen shell (Pinna nobilis), sea snail (Murex trunculus), golden grey mullet (Liza aurata) and black goby (Gobius niger) was evaluated, considering their distribution throughout the Mar Menor lagoon and their variations in spring and autumn 2010. The analytical procedure was adapted for the different matrices as being sensitive and reproducible. Eighteen out of the 20 compounds analysed were found at low ngg(-1) in these species throughout the lagoon. Hydrochlorothiazide and carbamazepine were detected in all species considered. The bioaccumulation of pharmaceuticals was heterogeneous in the lagoon, with a higher number of pharmaceuticals being detected in fish (18) than in wild molluscs (8), particularly in golden grey mullet muscle (16). В-blockers and psychiatric drugs were preferentially bioccumulated in fish and hydrochlorothiazide was also confirmed in caged clams. The higher detection frequency and concentrations found in golden grey mullet suggested that mugilids could be used as an indicator of contamination by pharmaceuticals in coastal areas. To the best of our knowledge, this is the first study that shows data about hydrochlorothiazide, levamisole and codeine in wild marine biota., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Ecosystem pollution due to the lack of or inefficient wastewater treatment coverage in small communities is still a matter of great concern, even in developed countries. This study assesses the seasonal performance of 4 different full-scale wastewater technologies that have been used in small communities (<2000 population equivalent) for more than 10 years in terms of emerging contaminant (EC), chemical oxygen demand (COD), total suspended solids (TSS) and NH4-N removal efficiency. The studied technologies, which were selected due to their widespread use, included two intensive treatment systems (an extended aeration system (AS) and a rotating biological contactor (RBC)) and two extensive treatment systems (a constructed wetland (CW) and a waste stabilization pond (WSP)), all located in north-eastern Spain. The studied compounds belonged to the groups of pharmaceuticals, sunscreen compounds, fragrances, antiseptics, flame retardants, surfactants, pesticides and plasticizers. The 25 ECs occurred in wastewater at concentrations ranging from undetectable to 80 μg L(-1). The average removal efficiency was 42% for the CW, 62% for the AS, 63% for the RBC and 82% for the WSP. All the technologies except the WSP system showed seasonal variability in the removal of ECs. The ecotoxicological assessment study revealed that, whilst all the technologies were capable of decreasing the aquatic risk, only the WSP yielded no risk in both seasons., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Starting from measured river concentrations, emission factors of 158 organic compounds out of 199 analyzed belonging to different groups of priority and emerging contaminants [pesticides (25), pharmaceuticals and hormones (81), perfluoroalkyl substances (PFASs) (18), industrial compounds (12), drugs of abuse (8) and personal care products (14)] have been estimated by inverse modeling. The Llobregat river was taken as case study representative of Mediterranean rivers. Industrial compounds and pharmaceuticals are the dominant groups (range of 10(4) mg·1000 inhab(-1)·d(-1)). Personal care products, pesticides, PFASs and illegal drugs showed a load approximately one order of magnitude smaller. Considered on a single compound basis industrial compounds still dominate (range of ca. 10(3) mg·1000 inhab(-1)·d(-1)) over other classes. Generally, the results are within the range when compared to previously published estimations for other river basins. River attenuation expressed as the percentage fraction of microcontaminants eliminated was quantified. On average they were around 60-70% of the amount discharged for all classes, except for PFASs, that are poorly eliminated (ca. 20% on average). Uncertainties associated with the calculated emissions have been estimated by Monte-Carlo methods (15,000 runs) and typically show coefficients of variation of ca. 120%. Sensitivities associated with the various variables involved in the calculations (river discharge, river length, concentration, elimination constant, hydraulic travel time and river velocity) have been assessed as well. For the intervals chosen for the different variables, all show sensitivities exceeding unity (1.14 to 3.43), tending to amplify the variation of the emission. River velocity and basin length showed the highest sensitivity value. Even considering the limitations of the approach used, inverse modeling can provide a useful tool for management purposes facilitating the quantification of release rates of chemicals into the aquatic environment., (Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.)

A fast, simple and robust method has been developed for the simultaneous determination of 23 pharmaceuticals (including some major metabolites) in bivalve mollusks. The analytes belong to eight different therapeutic groups: antibiotics, psychiatric drugs, analgesics/anti-inflammatories, tranquilizer, calcium channel blockers, diuretic, and prostatic hyperplasia. The method is based on pressurized liquid extraction (PLE) followed by solid phase extraction clean-up (SPE), and ultra performance liquid chromatography-triple quadrupole mass spectrometry (UHPL-MS/MS) for the identification and quantification of the target analytes. It has been developed and validated in three different species of bivalves: Crassostrea gigas (Pacific oyster), Mytilus galloprovincialis (Mediterranean mussel), and Chamelea gallina (striped venus clam). The majority of the compounds were extracted with a recovery between 40 and 115%. The developed analytical method allowed the determination of the compounds in the lower ng/g concentration levels. The relative standard deviation was under 12% for the intra-day and 20% inter-day analyses, respectively. Finally, the method was applied to oyster, clam and mussel samples collected from the Ebro delta, Spain. The most ubiquitous compounds detected were the psychiatric drug venlanfaxine and the antibiotic azithromycin, with the highest concentrations found in mussel (2.7ng/g dw) and oyster (3.0ng/g dw), respectively. To the best of our knowledge, this is the first time that azithromycin has been reported in environmental samples of marine biota., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The seasonal variations in the occurrence and distribution of pharmaceuticals were evaluated in seawater and sediment of Mar Menor lagoon from spring 2010 to winter 2011. A total of 20 pharmaceuticals in seawater and 14 in sediments were found at concentrations from low ngL(-)(1) up to 168ngL(-)(1) (azithromycin) in seawater and from low ngg(-1) up to 50.3ngg(-1) (xylazine) in sediments. Azithromycin, xylazine and metoprolol were the most ubiquitous compounds in seawater since they were found in all seawater samples collected. Seven compounds were quantified in both matrices: clarithromycin, erythromycin, hydrochlorothiazide, irbesartan, losartan, salicylic acid and valsartan. Seasonal distribution profiles revealed different sources of pollutants associated to both, El Albujón watercourse (which receives the input of a WWTP) and other non-controlled discharges, into the lagoon. In summer the highest concentrations in seawater for most of the pharmaceuticals were detected close to main touristic nuclei, probably as consequence of sources such as the excretion from bathers and/or other non-controlled discharges, these being significantly higher than in autumn and winter for antibiotics. On the contrary, the mean concentration of lorazepam was significantly higher in colder seasons than in warmer ones. Sulfamethoxazole, erythromycin and especially clarithromycin showed hazard quotients higher than 1 in seawater at some areas of this lagoon indicating a potential risk to aquatic organisms in such specific areas., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Cytostatic drugs, used in chemotherapy, are excreted unchanged by urine and feces or modified as metabolites. Elimination of these drugs in wastewater treatment plants (WWTPs) is often incomplete and residues reach surface water. Their presence in the natural environment depends on consumption patterns, excretion fraction and the effectiveness of the wastewater treatment. This study compiled the total consumption of cytostatic drugs in Catalonia (NE Spain) and provides data on the occurrence and risk of anticancer drugs in the aquatic environment by calculating predicted environmental concentrations (PECs). PECs were estimated using publicly available consumption data in the period of 2010-2012, published or calculated excretion values and wastewater elimination rates for a suite of 132 compounds. This allows predicting the range of concentrations in effluent wastewaters and receiving waters. Out of the 132 cytostatics, mycophenolic acid and hydroxycarbamide had a PEC value higher than 10ngL(-1). PECs were compared with MECs (measured environmental concentrations) to evaluate the reliability of the estimation. A risk assessment was conducted to determine the potential adverse effects of cytostatics in the environment. All the risk quotients calculated using EC50 in Daphnia magna were below 1, showing no significant risk., (Copyright © 2015 Elsevier Inc. All rights reserved.)

A multitude of pharmaceuticals enter surface waters via discharges of wastewater treatment plants (WWTPs), and many raise environmental and health concerns. Chemical fate models predict their concentrations using estimates of mass loading, dilution and in-stream attenuation. However, current comprehension of the attenuation rates remains a limiting factor for predictive models. We assessed in-stream attenuation of 75 pharmaceuticals in 4 river segments, aiming to characterize in-stream attenuation variability among different pharmaceutical compounds, as well as among river segments differing in environmental conditions. Our study revealed that in-stream attenuation was highly variable among pharmaceuticals and river segments and that none of the considered pharmaceutical physicochemical and molecular properties proved to be relevant in determining the mean attenuation rates. Instead, the octanol-water partition coefficient (Kow) influenced the variability of rates among river segments, likely due to its effect on sorption to sediments and suspended particles, and therefore influencing the balance between the different attenuation mechanisms (biotransformation, photolysis, sorption, and volatilization). The magnitude of the measured attenuation rates urges scientists to consider them as important as dilution when aiming to predict concentrations in freshwater ecosystems., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Daphnia magna individuals were transplanted across 12 sites from three Spanish river basins (Llobregat, Ebro, Jucar) showing different sources of pollution. Gene transcription, feeding and biochemical responses in the field were assessed and compared with those obtained in re-constituted water treatments spiked with organic eluates obtained from water samples collected at the same locations and sampling periods. Up to 166 trace contaminants were detected in water and classified by their mode of action into 45 groups that included metals, pharmaceuticals, pesticides, illicit drugs, and other industrial compounds. Physicochemical water parameters differentiated the three river basins with Llobregat having the highest levels of conductivity, metals and pharmaceuticals, followed by Ebro, whereas the Jucar river had the greatest levels of illicit drugs. D. magna grazing rates and cholinesterase activity responded similarly than the diversity of riparian benthic communities. Transcription patterns of 13 different genes encoding for general stress, metabolism and energy processes, molting and xenobiotic transporters corroborate phenotypic responses differentiated sites within and across river basins. Principal Component Analysis and Partial Least Square Projections to Latent Structures regression analyses indicated that measured in situ responses of most genes and biomarkers and that of benthic macroinvertebrate diversity indexes were affected by distinct environmental factors. Conductivity, suspended solids and fungicides were negatively related with the diversity of macroinvertebrates cholinesterase, and feeding responses. Gene transcripts of heat shock protein and metallothionein were positively related with 11 classes of organic contaminants and 6 metals. Gene transcripts related with signaling paths of molting and reproduction, sugar, protein and xenobiotic metabolism responded similarly in field and lab exposures and were related with high residue concentrations of analgesics, diuretics, psychiatric drugs, β blockers, illicit drugs, trizoles, bisphenol A, caffeine and pesticides. These results indicate that application of omic technologies in the field is a promising subject in water management., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The use of chemicals is continuously growing both in total amount as well as in a number of different substances, among which organic chemicals play a major role. Owing to the growing public awareness on the need of protecting both ecosystems and human health from the risks related to chemical pollution, an increasing attention has been drowned to risk assessment and prioritization of organic pollutants. In this context, the aims of this study were (a) to perform an environmental risk assessment for 200 organic micropollutants including both regulated and emerging contaminants (pesticides, alkylphenols, pharmaceuticals, hormones, personal care products, perflourinated compounds and various industrial organic chemicals) monitored in four rivers located in the Mediterranean side of the Iberian Peninsula, namely, the Ebro, Llobregat, Júcar and Guadalquivir rivers; and (b) to prioritize them for each of the four river basins studied, taking into account their observed concentration levels together with their ecotoxicological potential. For this purpose, a prioritization approach has been developed and a resulting ranking index (RI) associated with each compound. Ranking index is based on the measured concentrations of the chemical in each river and its ecotoxicological potential (EC50 values for algae, Daphnia sp. and fish). Ten compounds were identified as most important for the studied rivers: pesticides chlorpyriphos, chlorfenvinphos, diazinon, dichlofenthion, prochloraz, ethion carbofuran and diuron and the industrial organic chemicals nonylphenol and octylphenol that result from the biodegration of polyethoxylated alkyphenol surfactants. Also, further research into chronic toxicity of emerging contaminants is advocated., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The aim of this study is to evaluate the presence of perfluoroalkyl substances (PFASs) in the blood of 46 residents from Barcelona and to study the factors that affect exposure. Compounds analysed included perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorobutane sulfonate (PFBS), perfluorooctanoate acid (PFOA) and perfluorononanoate acid (PFNA). Blood was liquid-liquid extracted and PFASs were determined by liquid chromatography coupled to tandem mass spectrometry. Good recoveries (between 97 ± 14 and 105 ± 13 %) were obtained and method detection limits were from 0.03 to 0.07 ng mL(-1). ΣPFASs ranged from 0.11 to 4.37 ng mL(-1). PFOS was the main compound detected at 0.09-3.35 ng mL(-1), followed by PFOA and PFHxS. PFBS and PFNA were seldom detected. Working conditions, smoking and gender did not cause any significant differences among ΣPFASs levels in the blood while age and parity produced decreased concentrations. On the other hand, laboratory working conditions produced significant higher PFOA levels compared to the general population. Compared to other studies, the PFASs levels in blood from Barcelona residents is low (mean ΣPFASs of 1.67 ± 0.88 ng mL(-1)) and with little variation among the studied population.

In this study we characterised the ciprofloxacin-resistant strains isolated in biofilm and sediments from a wastewater treatment plant (WWTP) discharge point and its receiving river. We also examined the prevalence of qnrA, qnrB, qnrS and aac(6')-Ib-cr genes in these isolates and determined whether they harbour plasmid-encoded β-lactamases such as TEM, SHV and CTX-M. Moreover, antibiotic concentrations were also measured to evaluate the level of contamination of these pharmaceuticals in the sampling area. Antibiotics were found in the range of ng L(-1) in WWTP effluents, but most of them were no longer found in downstream river. However, some fluoroquinolones were detected in sediment downstream demonstrating their high persistence and their capacity to be retained in the river sediments. Most of the ciprofloxacin-resistant isolates belonged to the Gammaproteobacteria class and 17 of them, 8 (7.6%) from the first sampling and 9 (6.1%) from the second sampling, carried a qnr gene. In particular, 15 isolates carried the qnrS gene and 2 carried the qnrB gene. Among the qnr-positive isolates, 12 harboured the aac(6')-lb-cr gene and 2 of them also carried a β-lactamase on the same plasmid, indicating that they may be transferred simultaneously. It is also noteworthy that all qnr-positive isolates identified as Aeromonas species harboured the same qnrS allele, namely the qnrS2. This study reinforces the importance of environmental bacteria as vehicles for dissemination of antibiotic resistance genes., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The seasonal occurrence and distribution of 69 pharmaceuticals along coastal watercourses during 6 sampling campaigns and their input through El Albujón watercourse to the Mar Menor lagoon were determined by UPLC-MS-MS, considering a total of 115 water samples. The major source of pharmaceuticals running into this watercourse was an effluent from the Los Alcazares WWTP, although other sources were also present (runoffs, excess water from irrigation, etc.). In this urban and agriculturally influenced watercourse different pharmaceutical distribution profiles were detected according to their attenuation, which depended on physicochemical water conditions, pollutant input variation, biodegradation and photodegradation rates of pollutants, etc. The less recalcitrant compounds in this study (macrolides, β-blockers, etc.) showed a relevant seasonal variability as a consequence of dissipation processes (degradation, sorption, etc.). Attenuation was lower, however, for diclofenac, carbamazepine, lorazepam, valsartan, sulfamethoxazole among others, due to their known lower degradability and sorption onto particulate matter, according to previous studies. The maximum concentrations detected were higher than 1000 ng L(-1) for azithromycin, clarithromycin, valsartan, acetaminophen and ibuprofen. These high concentration levels were favored by the limited dilution in this low flow system, and consequently some of them could pose an acute risk to the biota of this watercourse. Considering data from 2009 to 2010, it has been estimated that a total of 11.3 kg of pharmaceuticals access the Mar Menor lagoon annually through the El Albujón watercourse. The highest proportion of this input corresponded to antibiotics (46%), followed by antihypertensives (20%) and diuretics (18%)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The concentrations of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylates, C4, C6-C8 and C10 sulfonates and C8 sulfonamide) were determined in influent, effluent and sludge from 16 different sewage treatment plants (STPs) located in the Ebro (6), Guadalquivir (5), Jucar (2) and Llobregat (3) Rivers, in two consecutive years (2010 and 2011). The analytes were extracted by solid phase extraction (SPE) and determined by Liquid Chromatography triple Quadrupole Mass Spectrometer (LC-QqQ-MS). All samples, except two sludges from Guadalquivir River STPs, were contaminated with at least one PFAS. Perfluorobutanoate (PFBA), perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (L-PFOS) were the most frequently detected. The highest concentration in water was determined in 2010 in a Guadalquivir River STP (perfluorohexanoate, PFHxA: 5.60μgL(-1)) and, in 2011, in an Ebro River STP (perfluorobutane sulfonate, L-PFBS: 0.31μgL(-1)). In sludge samples, the maximum concentration in 2010 was 1.79μgg(-1)dry weight (dw) (L-PFOS, in a Llobregat River STP), and in 2011, 1.88μgg(-1)dw (PFBA, in one Guadalquivir River STP). High PFAS values in sludge could be related to positive removal efficiencies, and can be attributed to their adsorption. Distribution coefficients (Kd) were determined ranging between 0.32Lkg(-1) (perfluorohexane sulfonate, L-PFHxS) and 36.6 10(3)Lkg(-1) (PFBA). The total PFAS loads discharged into the basins showed high values for the Ebro River STPs (66.9gday(-1)) while in the others, the loads were between 3.97gday(-1), in the Jucar STPs, and 32.2gday(-1), in the Guadalquivir STPs., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants such as hexabromobenzene (HBB), pentabromoetilbenzene (PBEB), decabromodiphenyl ethane (DBDPE), Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), Dechlorane 604 (Dec 604) and Dechlorane plus (DP) were analyzed in 33 sediments and 7 sludges from two Iberian river basins, Ebro and Llobregat. In sediment samples, PBDE levels ranged between nd and 44.3ng/g dw with BDE-209 being the most abundant congener. Levels of DBDPE and halogenated norbornenes ranged between nd and 31.5ng/g dw and between nq and 3.74ng/g dw, respectively. This is the first study to report halogenated norbornene levels in sediment samples from Spain. PBDE, DBDPE and halogenated norbornene levels in sludge ranged from 13 to 340, nq to 124 and 2.7 to 19ng/g dw, respectively. HBB and PBEB were not detected in any sample. Levels of classic and emerging HFRs were compared. Our results suggest that DBDPE is the most frequently used compound to replace BDE-209, whereas the use of halogenated norbornenes is still low., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Forty-eight fish samples from the Llobregat, Ebro, Júcar and Guadalquivir river basins (Spain), were analyzed for polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), pentabromoethylbenzene (PBEB) and halogenated norbornenes (HNs). The most contaminated river basin was the Llobregat, followed by the Ebro, Júcar and Guadalquivir for almost every analyzed contaminant. Most abundant PBDE congener was BDE-47 (BDL-396 ng/g lw) and the most abundant halogenated norbornene was Dechlorane-602 (BQL-174 ng/g lw). Fanti was calculated to determine the different bioaccumulation/biodegradation of syn-DP and anti-DP. Biota to sediment accumulation factor was calculated in order to compare the bioaccumulation capacity of emerging flame retardants with that of "classical" PBDEs. It was found that bioaccumulation of halogenated norbornenes is lower than that of PBDEs. BDE-99, HBB, PBEB and Dechlorane-604 were not detected in any sample., (Copyright © 2013 Elsevier B.V. All rights reserved.)

This paper describes the development and application of a multi-residue chiral liquid chromatography coupled with tandem mass spectrometry method for simultaneous enantiomeric profiling of 18 chiral pharmaceuticals and their active metabolites (belonging to several therapeutic classes including analgesics, psychiatric drugs, antibiotics, cardiovascular drugs and β-agonists) in surface water and wastewater. To the authors' knowledge, this is the first time an enantiomeric method including such a high number of pharmaceuticals and their metabolites has been reported. Some of the pharmaceuticals have never been studied before in environmental matrices. Among them are timolol, betaxolol, carazolol and clenbuterol. A monitoring programme of the Guadalquivir River basin (South Spain), including 24 sampling sites and five wastewater treatment plants along the basin, revealed that enantiomeric composition of studied pharmaceuticals is dependent on compound and sampling site. Several compounds such as ibuprofen, atenolol, sotalol and metoprolol were frequently found as racemic mixtures. On the other hand, fluoxetine, propranolol and albuterol were found to be enriched with one enantiomer. Such an outcome might be of significant environmental relevance as two enantiomers of the same chiral compound might reveal different ecotoxicity. For example, propranolol was enriched with S(-)-enantiomer, which is known to be more toxic to Pimephales promelas than R(+)-propranolol. Fluoxetine was found to be enriched with S(+)-enantiomer, which is more toxic to P. promelas than R(-)-fluoxetine.

The zebra mussel Dreissena polymorpha is a Caspian Sea bivalve that colonized freshwater bodies worldwide during the XX century. To analyze the impact of seasonal and environmental variations on the physiology and metabolism of this invasive species, we developed a custom microarray using 4057 publicly available DNA sequences from Dreissena and other related genera. Transcriptome profiles were analyzed using half-body samples from a relatively clean site (Riba-Roja, low Ebro River, N.E. Spain), at three different stages of the annual cycle: Pre-spawning (February), spawning (June), and gonad resorption (September). Transcripts from a total of 745 unique sequences showed significant changes among these three groups of samples. Functional characterization of these transcripts based on their closest known homologues showed that genes involved in stress defense (oxidative and infection) were overrepresented in September, whereas genes related to reproductive functions were overrepresented in the spawning and pre-spawning periods. This transcriptomic information can help to identify developmental stages at which the organism is more vulnerable for future control strategies. These data will also contribute to the implementation of gene expression-based assays for pollution monitoring in water bodies harboring stable zebra mussel populations., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The present work reports the occurrence of pharmaceuticals and their metabolites and transformation products (TPs) in the Ebro river basin (NE Spain). Twenty-four samples of water collected along the basin were analysed using a fully automated method based on on-line turbulent chromatography-liquid chromatography-tandem mass spectrometry (TFC-LC-MS/MS). In total, 17 metabolites, 7 of them with remaining pharmacologic activity, and 2 transformation products, along with 58 parent pharmaceuticals are analysed. Metabolites and TPs were found at concentrations of the same order of magnitude as their corresponding parent pharmaceuticals, with the exception of 10,11-epoxi-carbamazepine which was found at approximately 10 times higher concentration than its corresponding parent pharmaceutical carbamazepine. In general, levels of all target compounds were below 100 ng L(-1), with the exception of 14 compounds; among them the aforementioned 10,11-epoxicarbamazepine with a maximum concentration of more than 1600 ng L(-1). The analgesic propyphenazone, the psychiatric drug carbamazepine, the antibiotics clarithromycin and sulfadiazine, the cardiovascular drug propranolol, the antineoplastic tamoxifen and 1 pharmacologically active metabolite salicylic acid were found to be ubiquitous (detected in all samples). Smaller tributaries generally show higher concentrations than the main river Ebro, due to lower dilution of WWTP effluents discharged., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Perfluorinated compounds (PFCs) are persistent and bioaccumulative organic compounds used as additives in many industrial products. After use, these compounds enter wastewater treatment plants (WWTP) and long-chain PFCs are primarily accumulated in sludge. The aim of this study was to determine the occurrence and behavior of five PFCs in sludge from 15 WWTP from Spain and Germany that receive both urban and industrial wastes. The PFCs studied were perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), perfluorobutanesulfonate (PFBS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). One gram of freeze-dried, sieved, and homogenized sludge was extracted using an ultrasonic bath with methanol and glacial acetic acid. After that, the extract was recovered and evaporated to dryness with a TurboVap and then 1 mL of acetonitrile was added and the extract was cleaned up with black carbon. Liquid chromatography coupled to mass spectrometry operated in selected reaction monitoring was used to determine target compounds. Quality parameters are provided for the set of compounds studied. PFCs were detected in all samples. In Spanish sludge, ∑PFC ranged from 0.28 to 5.20 ng/g dry weight (dw) with prevalence of PFOS, while in German sludge, ∑PFC ranged from 20.7 to 38.6 ng/g dw and PFBS was the dominant compound. As a next step, the evolution of PFC concentrations within the sludge treatment steps (primary sludge, anaerobic digested sludge, and centrifuged sludge) was evaluated and differences among levels and patterns were observed and were attributed to the influent water quality and treatment used. Finally, we estimated the amount of PFCs discharged via sludge in order to determine the potential impact to the environment according to different sludge usage practices in the two regions investigated. This manuscript provided an intra-European overview of PFC distribution in sludge. Levels and compound distribution depend on the WWTP sampled. This study demonstrates that PFCs are persistent to sludge treatment and the loads in sludge may pose a future environmental risk, if not controlled.

Background, Aim and Scope: Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination., Materials and Methods: Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed., Results and Discussion: Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77-124 %) and limits of quantification were between 0.0004 and 0.029 μg/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018 μg/L for octylphenol to 0.970 μg/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115 μg/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds., Conclusions: Target compounds were detected in a very low concentration and only in very few samples. This indicates the good quality of source waters intended for bottling and the effectiveness of the protection measures adopted in Spain. None of the samples analysed exceeded the maximum legislated levels for drinking water both in Spain and in the European Union.

The aim of this study was to determine the impact of priority and emerging Persistent Organic Pollutants (POPs) in gull eggs from two species, the scavenger Larus michahellis and the protected species, Larus audouinii. These two species share habitat in the Natural Park of the Ebro delta (Catalonia, Spain). Compounds studied are included or under consideration in the Stockholm Convention and comprise polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorinated compounds (OCs), perfluorinated compounds (PFCs) and short chain chlorinated paraffins (SCCPs). Four methods based in selective extraction and gas or liquid chromatography coupled to mass spectrometry were used and quality parameters are provided. OC pesticides and marker PCBs were the most abundant chemical families detected in eggs from the two species, followed by PFCs, PBDEs (especially BDE 209) and SCCPs. Dioxin-like PCBs and PCDD/Fs were also detected in all samples. The overall widespread presence of POPs is discussed in terms of feeding habits, bird ecology and anthropogenic pressures in the protected Ebro delta breeding area., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The complex behavior observed for the dependence of trihalomethane formation on forty one water treatment plant (WTP) operational variables is investigated by means of linear and non-linear regression methods, including kernel-partial least squares (K-PLS), and support vector machine regression (SVR). Lower prediction errors of total trihalomethane concentrations (lower than 14% for external validation samples) were obtained when these two methods were applied in comparison to when linear regression methods were applied. A new visualization technique revealed the complex nonlinear relationships among the operational variables and displayed the existing correlations between input variables and the kernel matrix on one side and the support vectors on the other side. Whereas some water treatment plant variables like river water TOC and chloride concentrations, and breakpoint chlorination were not considered to be significant due to the multi-collinear effect in straight linear regression modeling methods, they were now confirmed to be significant using K-PLS and SVR non-linear modeling regression methods, proving the better performance of these methods for the prediction of complex formation of trihalomethanes in water disinfection plants., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Water has been identified as one of the main routes of human exposure to perfluoroalkyl substances (PFASs). This work assessed the presence of 21 PFASs along the whole water cycle using a new fast and cost effective analytical method based on an online sample enrichment followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method was validated for different types of matrices (ultrapure water, tap water and treated wastewater). The quality parameters for the 21 selected compounds presented good limits of detection (LOD) and quantification (LOQ) ranging, in general, from 0.83-10 ng/L to 2.8-50 ng/L, respectively. The method was applied to assess the occurrence of PFASs in 148 water samples of different steps along the whole water cycle, including: mineral bottled water, tap water, river water and treated effluent wastewater, from Germany to Spain. In addition, in order to prove the good performance of the online analytical method, the analysis of PFASs was carried out in parallel using a method based on offline anionic solid phase extraction (SPE) followed by LC-MS/MS. Consistent results were obtained using both approaches. The more frequently found compounds were perfluoroalkyl acids, such as the perfluorobutanoic acid which was in the 54% of the tap water samples investigated with concentrations in the range between 2.4 and 27 ng/L, the perfluoroheptanoic acid (0.23-53 ng/L) and perfluorooctanoic acid (0.16-35 ng/L), and the sulphonate perfluorooctanesulfonate (0.04-258 ng/L) which was the second more frequent compound and also the compound found in with the higher concentration. It should be remarked that the 88% of the samples analyzed presented at least one of the compounds at quantifiable concentrations. In addition, PFASs including short chain compounds were proved to be prevalent in drinking water, and the 50% of the drinking water samples showed quantifiable concentrations of PFASs. It should be said that the great majority of the samples may not pose an immediate health risk to consumers, and just 6 of the drinking water samples presented concentrations of PFOS exceeding the Provisional Health Advisory (PHA) level established by the Office of Water from the USEPA for PFOS, which was set in 200 ng/L., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Introduction: Concentrations of alkylphenolic compounds (APCs) in water and sediments were related to the composition and functional descriptors of the benthic community (biofilm and macroinvertebrates)., Materials and Methods: Samples were collected in four sampling campaigns at seven sampling points in the lower Llobregat catchment area (NE Spain). Water and sediment samples underwent chemical target analysis for nine APCs, which are known to disrupt the endocrine system., Results and Discussions: APCs were the main stressors on the diatom community but not on the macroinvertebrate community., Conclusions: Benthic invertebrates were mostly affected by the general physicochemical water characteristics (where conductivity was a surrogate). Nonylphenol only had an influence on the diatom community in water but not in the remaining compartments, probably because of the low concentrations observed in the environment.

Purpose: The Llobregat River, which is characterized by important fluctuations of the flow rates, receives treated waters from WWTPs. During the years 2007 and 2008, the Llobregat River basin suffered from a severe drought which affected the supply of drinking water facilities (DWF) that rely on the exploitation of the river water. The Catalan Water Agency implemented a water reuse experiment with the objective of maintaining the river flow rate at sufficiently high level so as to ensure the supply of raw water to Barcelona's major DWF., Method: A total of 103 emerging contaminants belonging to the groups of pharmaceuticals (74), illicit drugs (17) and oestrogens (12) were determined using LC-MS/MS methods in river water samples during the water reuse campaign. The effect of the reclaimed water discharge on the river water quality, in terms of contamination loads and environmental risk (based on the concentration addition mode), is discussed., Results: Fifty-eight pharmaceuticals out of 74 monitored were detected at least in one sample. In river water upstream (site R0) majority of compounds were detected at low nanograms per litre levels, while downstream of discharge of tertiary effluent only few compounds were detected at levels higher than 100 ng L(-1) (i.e. acetaminophen, diclofenac, erythromycin, sulfamethazine), but never exceeding 500 ng L(-1). The total concentration of illicit drugs was found to be very low at both sampling sites (<50 ng L(-1)). No relevant ecotoxicity risks were identified, except for pharmaceuticals vs. algae., Conclusions: In general, the discharge of reclaimed water in the river influenced perceptibly in terms of concentrations, mass loads and environmental risk, especially for pharmaceuticals and in less extent for illicit drugs. Nevertheless, it was not very significant in any case.

Introduction: Mediterranean rivers are characterized by a high flow variability, which is strongly influenced by the seasonal rainfall. When water scarcity periods occur, water flow, and dilution capacity of the river is reduced, increasing the potential environmental risk of pollutants. On the other hand, floods contribute to remobilization of pollutants from sediments. Contamination levels in Mediterranean rivers are frequently higher than in other European river basins, including pollution by pharmaceutical residues. Little attention has been paid to the transport behavior of emerging contaminants in surface waters once they are discharged from WWTP into a river. In this context, this work aimed to relate presence and fate of emerging contaminants with hydrological conditions of a typical Mediterranean River (Llobregat, NE Spain)., Methods: River fresh water samples were collected twice a week over a period of 5 weeks at three sampling points. Sixty-six pharmaceutical compounds belonging to different therapeutical classes were analyzed by LC-MS/MS., Results and Discussion: Positive and negative correlations between the concentrations of the target analytes and hydrological variables like river flow and dissolved organic matter were observed pointing out the relevance of different hydrological phenomena like dilution effects or sediment re-suspension. Sensitivity calculations showed that the majority of compounds were sensitive to flow variations.

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)., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Concentrations of Mirex, Dechlorane (Dec) Plus (DP), Dec 602, Dec 603, and Dec 604 were significantly higher in peregrine falcon (Falco peregrinus) eggs from Canada than Spain, with the former having the only measurable concentrations of the dechlorinated DP products, decachloropentacyclooctadecadiene (aCl10DP) and undecachloropentacyclooctadecadiene (aCl11DP). Large variations also occurred in the in ovo concentrations of the DP monoadduct, DPMA. This is the first study to report the accumulation and metabolism of DP by peregrines, both DP and dechloranes in European biota, as well as dechloranes in a terrestrial organism and one at the top of the food web. The geographical differences in the measured in ovo concentrations reflect local exposure of the adult peregrines on their breeding grounds, likely differences in diet of the adults, the production of DP on the Niagara River, and the greater use of Mirex and dechloranes as flame retardants in North America than Europe.

Multiway and multiset data analysis extensions of the multivariate curve resolution alternating least squares (MCR-ALS) method are proposed for the investigation of the temporal distribution of the pollution by nitric oxide (NO) and ozone (O(3)) in one sampling station in the urban centre of Barcelona (Catalonia, Spain), during the years 2000-2006. Different specific studies were performed considering the annual and pluriannual contamination by these two contaminants, individually or in combination using different data matrix augmentation strategies and multiway and multiset data analysis models. Daily, hourly and annual profiles were estimated describing different patterns and summarising the main contamination processes. The daily and night trends found were mainly attributed to traffic and photochemical processes favoured by light radiation. Moreover, winter-summer seasonal trends were also clearly detected and their changes over different years assessed. The extension MCR-ALS method to multiset data analysis using different constraints like non-negativity, trilinearity and interaction among components is confirmed to be a powerful method to improve the interpretability of the different contamination patterns in atmospheric contamination studies.

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ngL(-1) range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals>alkylphenols>pesticides>illicit drugs≫estrogens., (Copyright © 2010 Elsevier Ltd. All rights reserved.)