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The study aimed to assess the occurrence and the environmental risk of a group of 51 selected pesticides in the Guadiana Basin (a biodiversity hotspot, in the Mediterranean). The most abundant pesticides were bentazone and 2,4-D, while terbuthylazine together with terbutryn constituted the most ubiquitous pesticides. Eighteen out of the 38 pesticides detected are no longer approved in Europe, and 5 of them are included in the list of priority substances. The risk assessment showed that azinphos ethyl, diflufenican, irganol, imidacloprid, and oxadiazon occurred occasionally, but always in concentrations above their respective ecotoxicological threshold value. Contrary, bentazone, terbuthylazine, and terbutryn presented a high risk in most of the sampled locations and periods. The site-specific risk assessment showed a spatial and temporal pattern, with a higher risk occurring mainly in intermittent streams, in the drought period. The presence of pesticides banned from the EU market since 2009 showed the importance of improving the monitoring process, to identify the main sources of pollution and the fate of these emerging compounds. The results showed the need of implementing actions to improve the sustainable use of pesticides in agricultural areas, working with farmers and management entities to reduce the contamination of aquatic ecosystems. Transboundary water governance is also required to solve potential transboundary contamination problems., he present research is co-funded by the European Union through the European Regional Development Fund, included in the COMPETE 2020 (Operational Program Competitiveness and Internationalization) through the ICT project (UIDB/04683/2020) with the reference POCI-01-0145-FEDER-007690, the ALOP project (ALT20-03-0145-FEDER-000004), and through the European Agricultural Fund for Rural Development through the FitoFarmGest Operational Group (PDR2020-101-030926). It has been partially funded also by the Spanish Ministry of Science and Innovation (Project CEX2018-000794-S) and the Government of Catalonia (2017 SGR 01404). LSMA acknowledges the support provided by the “National System of Youth Guarantee” contract within the National Operational programme on Youth Employment 2014-2020 (Youth Employment Initiative and the European Social Fund).

It is possible to consult this version in open access at the following web address: arXiv:2011.11578, The occurrence of polar pesticides in sediments has not been extensively investigated because of their relatively poor hydrophobicity and apparently less persistence in the environment. However, their continuous release into the aquatic systems calls for the evaluation of their potential accumulation in sediments and the role of this matrix as a potential source of these compounds. Considering this, a method based on pressurized liquid extraction (PLE), extract clean-up by solid phase extraction (SPE), and analyte determination by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated to analyze 50 relevant (frequently used and/or regulated or found in water) medium to highly polar pesticides in sediments. The method showed good performance regarding accuracy (relative recoveries between 76 and 124%), precision (relative standard deviation values < 20%), sensitivity (LODs in the low nanogram per gram for most compounds), linearity (coefficients of determination > 0.99), and matrix effects (negligible for all analytes). The use of an isotope dilution approach for quantification ensures result reliability. As a part of the validation process, the method was applied to the analysis of the target pesticides in sediments from the Llobregat River (NE Spain) showing the presence of five of them, namely, terbutryn, dichlorvos, terbuthylazine, diazinon, and irgarol. All 5 pesticides, due to both the concentrations found and their physical-chemical characteristics, demonstrate high potential for bioaccumulation and risk to aquatic organisms. Additional multi-disciplinary studies that investigate pesticide occurrence in different aquatic compartments and evaluate the potential risks for aquatic ecosystems are required to assess the environmental impact and significance of the presence of pesticides in sediments. [Figure not available: see fulltext.]. © 2019, Springer-Verlag GmbH Germany, part of Springer Nature., This work has received funding from the Government of Catalonia (2017 SGR 01404), the Spanish State Research Agency (AEI) and the European Regional Development Fund (ERDF) through the project BECAS (grant number CTM2016-75587-C2-2-R), and the European Union’s Horizon 2020 Research and Innovation Programme under grant agreement no. 727450.

Transport of hydrophobic pollutants in rivers such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and heavy metals is often facilitated by suspended sediment particles, which are typically mobilized during high discharge events. Suspended sediments thus represent a means of transport for particle related pollutants within river reaches and may represent a suitable proxy for average pollutant concentrations estimation in a river reach or catchment. In this study, multiple high discharge/turbidity events were sampled at high temporal resolution in the Globaqua River Basins Sava (Slovenia, Serbia), Adige (Italy), and Evrotas (Greece) and analysed for persistent organic pollutants such as PAHs (polycyclic aromatic hydrocarbons) or PCBs (polychlorinated biphenyls) and heavy metals. For comparison, river bed sediment samples were analysed as well. Further, results are compared to previous studies in contrasting catchments in Germany, Iran, Spain, and beyond. Overall results show that loadings of suspended sediments with pollutants are catchment-specific and relatively stable over time at a given location. For PAHs, loadings on suspended particles mainly correlate to urban pressures (potentially diluted by sediment mass fluxes) in the rivers, whereas metal concentrations mainly display a geogenic origin. By cross-comparison with known urban pressure/sediment yield relationships (e.g. for PAHs) or soil background values (for metals) anthropogenic impact – e.g. caused by industrial activities – may be identified. Sampling of suspended sediments gives much more reliable results compared to sediment grab samples which typically show a more heterogeneous contaminant distribution. Based on mean annual suspended sediment concentrations and distribution coefficients of pollutants the fraction of particle facilitated transport versus dissolved fluxes can be calculated. © 2018 The Authors, This work was supported by the 7th Framework Programme of the European Commission under Grant Agreement no 603629-ENV-2013-6.2.1-GLOBAQUA

There is a worldwide growing use of chemicals by our developed, industrialized, and technological society. More than 100,000 chemical substances are thus commonly used both by industry and households. Depending on the amount produced, physical-chemical properties, and mode of use, many of them may reach the environment and, notably, the aquatic receiving systems. This may result in undesirable and harmful side-effects on both the human and the ecosystem's health. Mediterranean rivers are largely different from Northern and Central European rivers in terms of hydrological regime, climate conditions (e.g. air temperature, solar irradiation, precipitation), and socio-economics (e.g. land use, tourism, crop types, etc.), with all these factors leading to differences in the relative importance of the environmental stressors, in the classes and levels of the pollutants found and their environmental fate. Furthermore, water scarcity might be critical in affecting water pollution because of the lowered dilution capacity of chemicals. This work provides raw chemical data from different families of microcontaminants identified in three selected Mediterranean rivers (the Sava, Evrotas, and Adige) collected during two sampling campaigns conducted in 2014 and 2015 in three different matrices, namely, water, sediments, and biota (fish). More than 200 organic micropollutants were analyzed, including relevant groups like pharmaceuticals, personal care products, perfluorinated compounds, pesticides, pyrethroid insecticides, flame retardants, and persistent organic pollutants. Data obtained were summarized with some basic statistics for all compound families and matrices analyzed. Observed occurrence and spatial patterns were interpreted both in terms of compound physical-chemical properties and local environmental pressures. Finally, their spatial distribution was examined and their ecotoxicological risk in the water phase was assessed. This allowed locating, at each basin, the most polluted sites (“hot spots”) and identifying the respective river basin specific pollutants (RBSPs), prioritizing them in terms of the potential ecotoxicological risk posed to the aquatic ecosystems., This work has been supported by the European Communities EU 7th Framework Programme Funding under Grant agreement no. 603629-ENV-2013-6.2.1-Globaqua and partly by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-01404) and by the Spanish Ministry of Science, Innovation and Universities (Projects CEX2018-000794-S and IBERAQUA-NET RED2018-102737-T). Special thanks are due to all partners of the GLOBAQUA consortium and the peer review panel for ensuring quality results and a fruitful collaboration within the frame of the project.

The management of the anthropogenic water cycle must ensure the preservation of the quality and quantity of water resources and their careful allocation to the different uses. Protection of water resources requires the control of pollution sources that may deteriorate them. This is a challenging task in multi-stressed catchments. This work presents an approach that combines pesticide occurrence patterns and stable isotope analyses of nitrogen (δ15N-NO3−, δ15N-NH4+), oxygen (δ18O-NO3−), and boron (δ11B) to discriminate the origin of pesticides and nitrogen-pollution to tackle this challenge. The approach has been applied to a Mediterranean sub-catchment subject to a variety of natural and anthropogenic pressures. Combining the results from both analytical approaches in selected locations of the basin, the urban/industrial activity was identified as the main pressure on the quality of the surface water resources, and to a large extent also on the groundwater resources, although agriculture may play also an important role, mainly in terms of nitrate and ammonium pollution. Total pesticide concentrations in surface waters were one order of magnitude higher than in groundwaters and believed to originate mainly from soil and/or sediments desorption processes and urban and industrial use, as they were mainly associated with treated wastewaters. These findings were supported by the stable isotope results that pointed to an organic origin of nitrate in surface waters and most groundwater samples. Ammonium pollution observed in some aquifer locations is probably generated by nitrate reduction. Overall, no significant attenuation processes could be inferred for nitrate pollution. The approach presented here exemplifies the investigative monitoring envisioned in the Water Framework Directive., This work has received funding from the EU Horizon 2020 Research and Innovation Programme through the WaterProtect project (grant agreement No. 727450), the Spanish Ministry of Science and Innovation (Project CEX2018-000794-S), and the Generalitat de Catalunya (Consolidated Research Group 2017 SGR 01404-Water and Soil Quality Unit).

Data obtained from wastewater analysis can provide rapid and complementary insights in illicit drug consumption at community level. Within Europe, Spain is an important country of transit of both cocaine and cannabis. The quantity of seized drugs and prevalence of their use rank Spain at the top of Europe. Hence, the implementation of a wastewater monitoring program at national level would help to get better understanding of spatial differences and trends in use of illicit drugs. In this study, a national wastewater campaign was performed for the first time to get more insight on the consumption of illicit drugs within Spain. The 13 Spanish cities monitored cover approximately 6 million inhabitants (12.8% of the Spanish population). Untreated wastewater samples were analyzed for urinary biomarkers of amphetamine, methamphetamine, MDMA, cocaine, and cannabis. In addition, weekend samples were monitored for 17 new psychoactive substances. Cannabis and cocaine are the most consumed drugs in Spain, but geographical variations showed, for instance, comparatively higher levels of methamphetamine in Barcelona and amphetamine in Bilbao, with about 1-fold higher consumption of these two substances in such metropolitan areas. For amphetamine, an enantiomeric profiling was performed in order to assure the results were due to consumption and not to illegal dumping of production residues. Furthermore, different correction factors for the excretion of cannabis were used to compare consumption estimations. All wastewater results were compared with previously reported data, national seizure data and general population survey data, were a reasonable agreement was found. Daily and yearly drug consumption were extrapolated to the entire Spanish population with due precautions because of the uncertainty associated. These data was further used to estimate the retail drug market, where for instance cocaine illicit consumption alone was calculated to contribute to 0.2–0.5% of the Spanish gross domestic product (ca. 3000–6000 million Euro/year)., This study was supported by MINECO/AEI projects (CTM2016-81935-REDT, CTM2017-84763-C3-2-R, CTM2017-84763-C3-1-R, CTM2017-84763-C3-3-R, RTI2018-097158-B-C31 and CTM2017-90890-REDT), MICINN project (CEX2018-000794-S), Galician Council of Culture, Education and Universities (ED481D-2017/003, ED431C-2017/36 and ED481A-2020/258), cofounded by FEDER/ERDF. The UJI and CIDE (CSIC-UV-GV) authors acknowledge the financial support of Generalitat Valenciana (Excellence Research Group, Prometeo 2019/040 and Prometeo 2018/150, respectively). IDAEA-CSIC authors acknowledge the financial support of Generalitat de Catalunya (Exp. Num. SA-2018-780 and Consolidated Research Group 2017 SGR 01404) and the Spanish Ministry of Science and Innovation (Project CEX2018-000794-S). Alberto Celma acknowledges the Spanish Ministry of Economy and Competitiveness for his predoctoral Grant (BES-2016-076914). Elena Pitarch acknowledge the financial support of University Jaume I of Castellón, Spain (project UJI-B2018-55). Andreu Rico is supported by a postdoctoral grant provided by the Spanish Ministry of Science, Innovation and University (IJCI–2017–33465).

Phthalates are widely used plasticizers that produce endocrine-disrupting disorders. Quantifying exposure is crucial to perform risk assessments and to develop proper health measures. Herein, a wastewater-based epidemiology approach has been applied to estimate human exposure to six of the mostly used phthalates within the Spanish population. Wastewater samples were collected over four weekdays from seventeen wastewater treatment plants serving thirteen cities and ca. 6 million people (12.8 % of the Spanish population). Phthalate metabolite loads in wastewater were transformed into metabolite concentrations in urine and into daily exposure levels to the parent phthalates. Considering all the sampled sites, population-weighted overall means of the estimated concentrations in urine varied between 0.7 ng/mL and 520 ng/mL. Very high levels, compared to human biomonitoring data, were estimated for monomethyl phthalate, metabolite of dimethyl phthalate. This, together with literature data pointing to other sources of this metabolite in sewage led to its exclusion for exposure assessments. For the remaining metabolites, estimated concentrations were closer to those found in urine. Their 4-days average exposure levels ranged from 2 to 1347 μg/(day∙inh), exceeding in some sites the daily exposure thresholds set for di-i-butyl phthalate and di-n-buthyl phthalate by the European Food Safety Authority., Financial support. This study was supported by MCIU/AEI (projects CTM2016-81935-REDT, CTM2017-84763-C3-1-R, CTM2017-84763-C3-2-R, CTM2017-84763-C3-3-R, and CEX2018-000794-S), Galician Council of Culture, Education and Universities (ED481D 2017/003 and ED431C2017/36), Generalitat Valenciana (projects Prometeo/2018/155 and Prometeo/2019/040) and Universitat Jaume I (project UJI-B2018-55). Several of the above mentioned projects are cofunded by FEDER/ERDF. Sampling, sample and data provision and/or analytical support: Viaqua and Concello de Santiago de Compostela, EMAYA (Palma), Jordi Palatsi from Aqualia (Lleida WWTP), Cristian Mesa and Angela Vidal from Aigues de Barcelona (Barcelona WWTP), Iñigo González (Consorcio de Aguas de Bilbao-Bizkaia), the Public Entity of Wastewater Treatment (EPSAR) of the Generalitat Valenciana and especially Fernando Llavador. Luis Aceiton, Enrique Albors, Angel Jiménez, Maria José Tarrega, Sonia Tristante and all the personal of the WWTPs (Aguas de Valencia, Spain), are acknowledged for their help with the sampling. Sociedad de Fomento Agrícola Castellonense (FACSA, Castellon), and especially WWTP operators Santiago Querol and Sara Gargallo are acknowledged for providing wastewater samples from Castellón, as well as Subdirección General de Gestión del Agua, Ayuntamiento de Madrid, for allowing the collection of samples from Madrid centro.

The massive use of pesticides represents one of the main causes of environmental deterioration, as they have adverse effects on non-target organisms. Thus, the development of technologies capable of reducing their release into the environment is urgently needed. This study reports for the first time the white-rot fungus Trametes versicolor as an alternative towards the degradation of medium to highly polar pesticides such as the organophosphate malathion, and the neonicotinoids acetamiprid and imidacloprid. Specifically, T. versicolor could completely remove 1 mg/L of malathion in an Erlenmeyer flask within 48 h, while experiments of acetamiprid and imidacloprid (4 mg/L), conducted in air-pulse fluidized bioreactors, resulted in degradation percentages of 20% and 64.7%, respectively, after 7 days of operation. Enzymatic exploration studies revealed that the cytochrome P450 system, instead of the extracellular enzyme laccase, is involved in the degradation of acetamiprid and imidacloprid. The degradation pathways were proposed based on the main transformation products (TPs) formed in the solutions: seven in the case of malathion, and two and one in the case of imidacloprid and acetamiprid, respectively. Although the TPs identified were predicted to be less toxic than the investigated pesticides, the toxicity of the individual solutions slightly increased throughout the degradation process, according to the Microtox assay. However, the solution toxicity was always below the threshold established in the local regulation. Although additional research is needed to implement this treatment at a pilot plant scale, this work highlights the potential of T. versicolor to bio-remediate pesticide-contaminated waters., This work has been supported by the Spanish Ministry of Economy and Competitiveness State Research Agency (CTM2016-75587-C2-1-R and CTM2016-75587-C2-2-R) and co-financed by the European Union through the European Regional Development Fund (ERDF) and the Horizon 2020 research and innovation WATERPROTECT project (727450). This work was partly supported by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-01404) and the Ministry of Science and Innovation (Project CEX2018-000794-S). The Department of Chemical, Biological, and Environmental Engineering of the Universitat Autònoma de Barcelona is a member of the Xarxa de Referència en Biotecnologia de la Generalitat de Catalunya. K. Hu acknowledges the financial support from the Chinese Scholarship Council.

The study of the presence in the aquatic environment of certain substances considered as contaminants of emerging concern (CEC) is a preliminary step to the analysis of the possible harmful effects on aquatic ecosystems and the establishment of the corresponding environmental quality standards. In order to monitor the occurrence of CECs in the aquatic environment, the European Commission established in 2015 and 2018 two watch-list of substances for Union-wide monitoring in the field of water policy (Decision (EU) 2015/495 and Decision (EU) 2018/840). In the coast of the Basque Country, southeast of the Bay of Biscay, 19 of these watch list substances were monitored quarterly from May 2017 to March 2019. Water samples were collected at the effluent of three wastewater treatment plants and five control points associated with receiving waters (transitional and coastal water bodies). The most frequently quantified substances were azithromycin (91%), imidacloprid (82%), clarithromycin (80%), diclofenac (78%) and erythromycin (73%), with frequencies of quantification higher in wastewaters (83–100%) than in receiving waters (70–85%). In general, concentrations in wastewater were also higher than in receiving waters, indicating a dilution effect in the environment. In receiving waters, six out of the nineteen substances monitored exceeded their respective Predicted No-Effect Concentrations: azithromycin (34%), imidacloprid (9%), 17β-estradiol (E2) (9%), clarithromycin (7%), ciprofloxacin (7%), and diclofenac (5%); and therefore, their levels could pose an environmental risk., This work was supported by the Basque Water Agency (URA) through the project “Network for monitoring the ecological and chemical status of transitional and coastal waters of the Basque coast”, and partly by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-14) and the Ministry of Science and Innovation of Spain (Project CEX2018-000794-S). Biotage is acknowledged for the gift of ISOLUTE® Na2SO4 drying cartridges. The authors acknowledge the help of the entities in charge of the management of the three studied WWTPs (Consorcio de Aguas Bilbao Bizkaia, Consorcio de Aguas de Busturialdea and Aguas del Añarbe), as well as the work of all sampling and laboratory technicians. This is contribution number 1002 from the Marine Research of AZTI-BRTA (Basque Research and Technology Alliance).

It is possible to consult this version in open access at the following web address: arXiv:2011.11638, The occurrence of the extensively used herbicide diuron in the environment poses a severe threat to the ecosystem and human health. Four different ligninolytic fungi were studied as biodegradation candidates for the removal of diuron. Among them, T. versicolor was the most effective species, degrading rapidly not only diuron (83%) but also the major metabolite 3,4-dichloroaniline (100%), after 7-day incubation. During diuron degradation, five transformation products (TPs) were found to be formed and the structures for three of them are tentatively proposed. According to the identified TPs, a hydroxylated intermediate 3-(3,4-dichlorophenyl)-1-hydroxymethyl-1-methylurea (DCPHMU) was further metabolized into the N-dealkylated compounds 3-(3,4-dichlorophenyl)-1-methylurea (DCPMU) and 3,4-dichlorophenylurea (DCPU). The discovery of DCPHMU suggests a relevant role of hydroxylation for subsequent N-demethylation, helping to better understand the main reaction mechanisms of diuron detoxification. Experiments also evidenced that degradation reactions may occur intracellularly and be catalyzed by the cytochrome P450 system. A response surface method, established by central composite design, assisted in evaluating the effect of operational variables in a trickle-bed bioreactor immobilized with T. versicolor on diuron removal. The best performance was obtained at low recycling ratios and influent flow rates. Furthermore, results indicate that the contact time between the contaminant and immobilized fungi plays a crucial role in diuron removal. This study represents a pioneering step forward amid techniques for bioremediation of pesticides-contaminated waters using fungal reactors at a real scale., This work has been supported by the Spanish Ministry of Economy and Competitiveness State Research Agency (CTM2016-75587-C2-1-R and CTM2016-75587-C2-2-R) and co-financed by the European Union through the European Regional Development Fund (ERDF) and the Horizon 2020 research and innovation WATERPROTECT project (727450). This work was partly supported by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-14) and the Ministry of Science and Innovation (Project CEX2018-000794-S). The Department of Chemical, Biological and Environmental Engineering of the Universitat Autònoma de Barcelona is a member of the Xarxa de Referència en Biotecnologia de la Generalitat de Catalunya. K. Hu acknowledges the financial support from the Chinese Scholarship Council.

Occurrence of pharmaceuticals in the aquatic environment is nowadays a well-established issue that has become a matter of both scientific and public concern. Tons of different classes of pharmaceuticals find their way to the environment at variable degrees, after their use and excretion through wastewater and sewage treatment systems. The main goal of this study was to correlate the dynamics and the environmental risk of pharmaceuticals with different temporal and hydrological patterns, at the Guadiana Basin (South of Portugal). Water samples were collected bimonthly during 2017 (classified as a drought year) and 2018 (post-drought year) in: Zebro, Álamos and Amieira (intermittent hydrological streams), and Lucefécit (perennial hydrological stream). The pharmaceuticals quantified in higher concentrations, out of 27 investigated, were diclofenac (up to 4806 ng L−1), ibuprofen (3161 ng L−1), hydrochlorothiazide (2726 ng L−1) and carbamazepine (3223 ng L−1). Zebro and Álamos presented the highest contamination by this group of environmental hazardous substances, which may be correlated with the presence of wastewater treatment plants upstream the sampling point of each stream. Furthermore, the highest concentrations occurred mainly during the dry period (2017), when the flow was nearly inexistent in Zebro, and in Álamos after the first heavy rainfalls. In specific periods, the high concentrations of pharmaceuticals detected may induce risk for the organisms of lowest trophic levels, damaging the balance of the ecosystems at these streams. The risk quotient optimised approach (RQf) integrating exposure, toxicity and persistence factors, ranks the pharmaceuticals investigated in terms of risk for the aquatic ecosystems as follows: diclofenac, ibuprofen and carbamazepine (high risk), clarithromycin (moderate risk), acetaminophen, ofloxacin and bezafibrate (endurable risk), and hydrochlorothiazide (negligible risk)., The present research is co-funded by the European Union through the European Regional Development Fund, included in the COMPETE 2020 (Operational Program Competitiveness and Internationalization) through the ICT project (UID/GEO/04683/2013) with the reference POCI-01-0145-FEDER-007690, the ALOP project (ALT20-03-0145-FEDER-000004), and through the Engage SKA (POCI-01-0145-FEDER-022217) and by the European Union through the EU FP7 project SOLUTIONS (603437).

Cytostatic drugs and their metabolites enter the aquatic environment mainly through the excretion of urine and faeces from chemotherapy patients into the public sewer system and can eventually reach tap water if they are not properly eliminated during waste and drinking water treatment processes. Chlorine is globally the most used chemical disinfectant in wastewater treatment plants as well as in the pretreatment of hospital effluents prior to their discharge into the public sewage system, mostly because of its low cost. Since aqueous chlorine is not capable of complete mineralization of many anthropogenic compounds, numerous disinfection by-products may be formed due to oxidation/substitution reactions. Such reactions can happen during wastewater treatment processes and due to the discharge of chlorinated waters (e.g., tap water) or bleach into the sewage system. Very little is also known about their potential transformation into other chemical species, which might be even more toxic than the parent drugs. In recent years, several studies have demonstrated that anticancer drugs can yield a series of by-products when they come in contact with aqueous chlorine. Understanding the chemical fate of these by-products is an important first step to understand their environmental significance. Therefore, the main aim of this chapter is to comprehensively review the existing literature on the reactivity of anticancer drugs in the presence of free chlorine and the formation of their by-products.

Wastewater-based epidemiology (WBE) has become a very useful tool to monitor a population's drug consumption or exposure to environmental and food contaminants. In this work, WBE has been applied to estimate tobacco consumption in seven Spanish regions. To this end, 24 h composite wastewater samples were taken daily for one week in 17 wastewater treatment plants, covering altogether a population of ca. 6 million inhabitants. The samples were treated by enzymatic deconjugation and the wastewater content of two human-specific nicotine metabolites (namely, cotinine and trans-3′-hydroxycotinine) was measured to estimate the daily consumption of nicotine. The population-weighted average nicotine consumption in the seven analyzed regions was 2.2 g/(day∙1000 inh.), without any daily pattern. This average estimated nicotine consumption value agreed with the value derived from official tobacco sales data. Differences in consumption among the seven studied regions were found, being Galicia, the region with the lowest rate, and the Basque Country and Catalonia those with the highest rates. However, no conclusive correlation was found between those values and the prevalence data taken from two different national surveys, nor sociodemographic and health data. This study demonstrates that this tool can complement other indicators in order to accurately assess tobacco consumption rates at regional and national levels and provides the most extensive application of the approach in the Spanish territory., Financial support This study was supported by MINECO/AEI projects (CTM2016-81935-REDT, CTM2017-84763-C3-2-R, CTM2017-84763-C3-1-R, CTM2017-84763-C3-3-R), MICINN project (CEX2018-000794-S), Galician Council of Culture, Education and Universities (ED481D 2017/003 and ED431C2017/36), cofunded by FEDER/ERDF.

Background and aims Wastewater‐based epidemiology is an additional indicator of drug use that is gaining reliability to complement the current established panel of indicators. The aims of this study were to: (i) assess spatial and temporal trends of population‐normalized mass loads of benzoylecgonine, amphetamine, methamphetamine and 3,4‐methylenedioxymethamphetamine (MDMA) in raw wastewater over 7 years (2011–17); (ii) address overall drug use by estimating the average number of combined doses consumed per day in each city; and (iii) compare these with existing prevalence and seizure data. Design Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to 2017. Setting and Participants Catchment areas of 143 wastewater treatment plants in 120 cities in 37 countries. Measurements Parent substances (amphetamine, methamphetamine and MDMA) and the metabolites of cocaine (benzoylecgonine) and of Δ9‐tetrahydrocannabinol (11‐nor‐9‐carboxy‐Δ9‐tetrahydrocannabinol) were measured in wastewater using liquid chromatography–tandem mass spectrometry. Daily mass loads (mg/day) were normalized to catchment population (mg/1000 people/day) and converted to the number of combined doses consumed per day. Spatial differences were assessed world‐wide, and temporal trends were discerned at European level by comparing 2011–13 drug loads versus 2014–17 loads. Findings Benzoylecgonine was the stimulant metabolite detected at higher loads in southern and western Europe, and amphetamine, MDMA and methamphetamine in East and North–Central Europe. In other continents, methamphetamine showed the highest levels in the United States and Australia and benzoylecgonine in South America. During the reporting period, benzoylecgonine loads increased in general across Europe, amphetamine and methamphetamine levels fluctuated and MDMA underwent an intermittent upsurge. Conclusions The analysis of wastewater to quantify drug loads provides near real‐time drug use estimates that globally correspond to prevalence and seizure data., This study was supported by the following countries, institutions and projects Australia: Thyne Reid foundation; Canada: Natural Sciences and Engineering Research Council of Canada (NSERC); Iceland: The Icelandic Research Fund (Grant number 163049–051); Slovenia: Slovene Research Agency (funding Project L1–9191); Spain: MINECO/AEI projects (CTM2014–56628‐C3–2‐R, CTQ2015–65603‐P, CTM2016–81935‐REDT, CTM2017–84763‐C3–2‐R), Galician Council of Culture, Education and Universities (ED481D 2017/003); UK: Environmental Sustainability Knowledge Transfer Network, Engineering and Physical Sciences Research Council and Thermo Fisher Scientific (CASE industrial scholarship for K. Munro, Ref.: EP/J502029/1). European Monitoring Centre for Drugs and Drug Addiction (EMCDDA); EU International Training Network SEWPROF (Marie Curie‐FP7‐PEOPLE, grant number 317205); COST Action ES1307 supported by COST (European Cooperation in Science and Technology); WATCH (Wastewater Analysis of Traces of illicit drug‐related Chemicals for law enforcement and public Health DG migration and Home affairs ‐ HOME/2015/ISFP/PR/DRUG/0062). Sampling support and provision of catchment information Austria: Klemens Geiger and Michael Schlapp; Belgium: Jonathan Phariseau, Bart Coene, Luc Van Os, Peter Nys, Dieter Lemaire, Jean‐François Mougel, Patrick Vantroyen and Karel Claes; Croatia: Marin Ganjto; Czech Republic: Jiri Stara and Robert Hrich Brněnské; France: Véronique Bremont; Italy: Roberto Mazzini and Francesca Pizza (Milan), Francesco Avolio (Bologna), Fabrizio Moratto and Sergio Ghezzi (Gorizia), Rosanna Brienza and Simona Panariello (Potenza), Pier Paolo Abis and Antonia Attanasio (Bari), Antonella Cicala (Palermo); Norway: Pia Ryrfors; Portugal: João Goulão, José Martins, Pedro Alvaro and Fátima Paixão; Slovakia: Silvia Antalová and Jozef Tichy; Spain: Begoña Martínez López, Cristian Mesa, Santiago Querol Rodriguez, Fernando Llavador, Enrique Albors and Gloria Fayos; the Netherlands: Alex Veltman, Peter Theijssen, Peter van Dijk, Stefan Wijers, Mark Stevens, Ferry de Wilde. Analytical support Australia: Maulik Ghetia; Cyprus: Popi Karaolia; Greece: Nikoilaos Raikos; Spain: Ana Maria Botero‐Coy, Clara Boix, Alberto Celma, Jorge Pitarch, Inés Racamonde and Eddie Fonseca; Italy: Emma Gracia‐Lor, Nikolaos I. Rousis and Noelia Salgueiro‐Gonzalez. Data repository and data screening Eawag: Harald von Waldow; EMCDDA: Renate Hochwieser, Liesbeth Vandam, João Matias and Federica Mathis.

El análisis de aguas residuales con fines epidemiológicos es actualmente una herramienta fiable y complementaria a las metodologías basadas en indicadores tradicionales para el control de diferentes sustancias entre las que cabe destacar las drogas. Si bien varios países europeos la utilizan como herramienta de trabajo para la monitorización de drogas de abuso, en España su uso se limita principalmente a estudios realizados por diferentes grupos de investigación, tal y como se describe en el caso práctico puesto de ejemplo en el artículo. Sin embargo, el potencial de la metodología ha quedado evidenciado en los estudios científicos llevados a cabo tanto a nivel español como internacional y, aunque son necesarios más estudios para llegar a conocer todo su potencial, se prevé pueda ser incorporada como herramienta de trabajo complementaria a las que habitualmente se utilizan. En este sentido, la Red Española de Análisis de Aguas Residuales (ESAR-Net), creada en 2017 y formada por diferentes grupos de investigación españoles, pretende contribuir al conocimiento y aplicación de esta metodología en España a través de actividades científicas y de divulgación., Este estudio ha sido financiado por la Agencia Estatal de Investigación (AEI) a través del programa Redes de Excelencia (CTM2016-81935-REDT).

It is possible to consult this version in open access at the following web address: arXiv:2011.11639, Water is an essential resource for all living organisms. The continuous and increasing use of pesticides in agricultural and urban activities results in the pollution of water resources and represents an environmental risk. To control and reduce pesticide pollution, reliable multi-residue methods for the detection of these compounds in water are needed. In this context, the present work aimed at providing an analytical method for the simultaneous determination of trace levels of 51 target pesticides in water and applying it to the investigation of the target pesticides in two agriculture-impacted areas of interest. The method developed, based on an isotopic dilution approach and on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry, is fast, simple, and to a large extent automated, and allows the analysis of most of the target compounds in compliance with European regulations. Application of the method to the analysis of selected water samples collected at the lowest stretches of the two largest river basins of Catalonia (NE Spain), Llobregat and Ter, revealed the presence of a wide suite of pesticides in the Llobregat basin, some of them at concentrations above the water quality standards (irgarol and dichlorvos) or the acceptable method detection limits (methiocarb, imidacloprid, and thiacloprid), and much cleaner waters in the Ter River basin. Risk assessment of the pesticide concentrations measured in the Llobregat River indicated high risk due to the presence of irgarol, dichlorvos, methiocarb, azinphos ethyl, imidacloprid, and diflufenican (hazard quotient (HQ) values>10), and moderate potential risk in the Ter River, associated to the occurrence of bentazone and irgarol (HQ > 1)., This work has received funding from the European Union's Horizon 2020 - Research and Innovation Framework Programme (WaterProtect project, No. 727450), the Spanish State Research Agency (AEI) and the European Regional Development Fund (ERDF) (BECAS project, CTM2016-75587-C2-2-R), the Spanish Ministry of Science and Innovation (Project CEX2018-000794-S), and the Government of Catalonia (2017 SGR 01404). Vinyet Solà from CUADLL and Francesc Camps Saguè from IRTA are acknowledged for their help in the collection of samples from the Llobregat River and the Ter River, respectively.

Delta ecosystems are areas of high ecologic and economic values, where wildlife commonly shares the territory with intensive agricultural activities, particularly, rice cultivation and seafood production. This work aimed at evaluating the occurrence of a wide spectrum of pesticides and transformation products in the water of irrigation and drainage channels of the Ebro River Delta (NE Spain) during the main rice-growing season, when pesticide application is at its peak. Furthermore, the impact that these contaminants may have on local ecosystems and seafood production activities was assessed. A total of 35 pesticides, mainly associated with rice cultivation, out of the 66 analyzed were detected. Bentazone, propanil, MCPA, acetamiprid, and triallate were found at the μg/L level. Cybutryne was measured for the first time in the area and at concentrations above its environmental quality standard (11-49 ng/L), despite being banned in the European Union. Sixteen additional banned pesticides were also detected at trace levels, likely due to their desorption from soil and sediment particles. Bentazone, cybutryne, dicofol, imidacloprid, MCPA, and propanil posed a moderate to high risk for aquatic organisms at the normal concentration levels measured during the rice-growing season. The co-occurrence of pesticides may pose a high risk for aquatic organisms in all sampling locations. Despite its dilution when discharged into the bay, this study demonstrates that the agricultural use of pesticides may have important effects on water quality and may pose a serious hazard for aquatic non-target organisms, despite other factors such as temperature and salinity may play also a relevant role in pesticide toxicity. The finding of imidacloprid and acetamiprid, including in the Watch List, at concentrations above their maximum acceptable method detection limit, calls for control of their use and revision of their legal status., This work has received funding from the Government of Catalonia (2017 SGR 01404), the Spanish Ministry of Science and Innovation (Project CEX2018-000794), the Spanish State Research Agency (AEI) and the European Regional Development Fund (ERDF) through the project BECAS (grant number CTM2016-75587-C2-2-R). IRTA members acknowledge the support from CERCA Programme/Generalitat de Catalunya.

Background In this study, an alternative and complementary method to those approaches currently used to estimate alcohol consumption by the population is described. This method, known as wastewater-based epidemiology (WBE), allows back-calculating the alcohol consumption rate in a given population from the concentrations of a selected biomarker measured in wastewater. Methods Composite (24-h) wastewater samples were collected at the inlet of 17 wastewater treatment plants located in 13 Spanish cities for seven consecutive days in 2018. The sampled area covered 12.8% of the Spanish population. Wastewater samples were analyzed to determine the concentration of ethyl sulfate, the biomarker used to back-calculate alcohol consumption. Results Alcohol consumption ranged from 4.5 to 46 mL/day/inhabitant. Differences in consumption were statistically significant among the investigated cities and between weekdays and weekends. WBE-derived estimates of alcohol consumption were comparable to those reported by its corresponding region in the Spanish National Health Survey in most cases. At the national level, comparable results were obtained between the WBE-derived annual consumption rate (5.7 ± 1.2 L ethanol per capita (aged 15+)) and that reported by the National Health Survey (4.7 L ethanol per capita (aged 15+)). Conclusions This is the largest WBE study carried out to date in Spain to estimate alcohol consumption rates. It confirms that this approach is useful for establishing spatial and temporal patterns of alcohol consumption, which could contribute to the development of health care management plans and policies. Contrary to established methods, it allows obtaining information in a fast and relatively economical way., The authors would like to acknowledge all the city councils of the cities participating in this study for their collaboration as well as the operators of the WWTPs for their assistance in the collection of the wastewater samples, especially to: Cristian Mesa and Angela Vidal from Aigues de Barcelona (Barcelona WWTP), Jordi Palatsi from Aqualia (Lleida WWTP), Viaqua and Concello de Santiago de Compostela, the Public Entity of Wastewater Treatment (EPSAR) of the Generalitat Valenciana and especially to Fernando Llavador. Luis Aceiton, Enrique Albors, Angel Jiménez, Maria José Tarrega, Sonia Tristante and all the personal of the WWTPs (Aguas de Valencia, Spain), Sociedad de Fomento Agrícola Castellonense (FACSA, Castellón), and especially WWTP operators Santiago Querol and Sara Gargallo are acknowledged for providing wastewater samples from Castellón, as well as Subdirección General de Gestión del Agua, Ayuntamiento de Madrid, for allowing the collection of samples from Madrid.

This study aimed to evaluate the presence of ultraviolet filters (UV-Fs), benzotriazoles, pyrethroids and per- and polyfluoroalkyl substances (PFASs) in freshwater and wastewater from the northern Antarctic Peninsula region. All water samples analyzed contained UV-Fs residues and high concentrations were detected in anthropogenic impacted sites (< LOD up to 1300 ng/L). Likewise, benzotriazoles were detected in all water samples (< LOQ–920 ng/L). Regarding suspended particulate matter, almost all UV-Fs and all benzotriazoles were measured at concentrations ranging from < LOQ to 33 µg/g dry weight. Pyrethroids were also detected (< LOQ–250 ng/L) and their presence implies the existence of a gateway to the Antarctica Peninsula from other regions. The data confirmed the presence of PFASs (< LOD–7500 ng/L) in this area, in agreement with previous studies. In light of these results, extended monitoring in Antarctica should be carried out to perform a reliable environmental risk assessment leading to propose recommendations to minimize the anthropic impact., This research was supported by projects CTM2011-26372, CTM2013-57119, and CTM2014-57119-R of the Spanish National R+D Plan, and PICTO 2005N36155 of the Secretariat for Science and Technology and the Argentine Antarctic Institute. This study also received funding from the Generalitat de Catalunya (Consolidated Research Group “2017 SGR 01404—Water and Soil Quality Unit”) and from the European Union’s Seventh Framework Program for research, technological development, and demonstration under Grant Agreement No. 603437. This research is part of POLARCSIC activities. It reflects only the authors’ views. The Community is not liable for any use that may be made of the information contained therein. The authors would like to thank the logistical support provided by the Spanish, Argentinean, and Chilean Antarctic programs for conducting the fieldwork. The reviewers and editor are also acknowledged for their contribution to improve the article.

It is possible to consult this version in open access at the following web address: arXiv:2011.11546, The present study evaluated the capacity of a semi-closed, tubular horizontal photobioreactor (PBR) to remove pesticides from agricultural run-off. The study was carried out in July to study its efficiency under the best conditions (highest solar irradiation). A total of 51 pesticides, including 10 transformation products, were selected and investigated based on their consumption rate and environmental relevance. Sixteen of them were detected in the agricultural run-off, and the estimated removal efficiencies ranged from negative values, obtained for 3 compounds, namely terbutryn, diuron and imidacloprid, to 100%, achieved for 10 compounds. The acidic herbicide MCPA was removed by 88% in average, and the insecticides 2,4-D and diazinon showed variable removals, between 100% and negative values. The environmental risk associated to the compounds still present in the effluent of the PBR was evaluated using hazard quotients (HQs), calculated using the average and highest measured concentrations of the compounds. HQ values > 10 (meaning high risk) were obtained for imidacloprid (21), between 1 and 10 (meaning moderate risk) for 2,4-D (2.8), diazinon (4.6) and terbutryn (1.5), and, This research was funded by European Union's Horizon 2020 research and innovation program within the framework of the INCOVER project (GA 689242) and WATERPROTECT project (727450); by the Spanish Ministry of Science, Innovation and Universities, the Research National Agency (AEI), and the European Regional Development Fund (FEDER) within the project AL4BIO (RTI2018-099495-B-C21), and by the Government of Catalonia (Consolidated Research Group 2017 SGR 01404-Water and Soil Quality Unit). M.J. García-Galán, E. Uggetti and R. Díez-Montero would like to thank the Spanish Ministry of Economy and Competitiveness for their research grants (IJCI-2017-34601, RYC2018-025514-I and FJCI-2016-30997, respectively).