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Trabajo presentado en la 1ª Jornada sobre Contaminación por Pásticos, celebrada en Barcelona (España) del 27 al 28 de octubre de 2020., Estimating exposure to phthalate plasticizers is crucial to perform appropriate risk assessment and develop control measures. In this study, we analyze wastewater to estimate the exposure to six phthalates within thirteen Spanish cities. Composite daily samples were collected over four consecutive days in Spring 2018 at seventeen wastewater treatment plants serving ca. 6 million people. Concentrations of phthalate metabolites were converted into population-normalized loads and used to estimate (i) metabolite levels in urine, and (ii) values of daily exposure to the parent phthalates. Population-weighted means of the estimated concentrations in urine varied between 0.7 ng/mL and 520 ng/mL. Compared to human biomonitoring data, very high levels were obtained for monomethyl phthalate, metabolite of dimethyl phthalate. This fact, together with literature data pointing to other sources of this metabolite in sewage led to its exclusion for exposure assessment. As for the remaining metabolites, results obtained on a local scale revealed the butylated phthalates as the ones posing the highest concern, particularly for toddlers. On a national scale, including all the sampled sites, di-(2-ethylhexyl) phthalate accounted for the highest percentage of total risk, followed closely by diethyl phthalate and di-iso-butyl phthalate., MCIU/AEI (projects CTM2016-81935-REDT, 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)

Resumen del trabajo presentado en el SETAC Europe 30th Annual Meeting, celebrado en modalidad virtual del 3 al 7 de mayo de 2020., Wastewater provides a fingerprint of a specific population lifestyle. Tracing the right chemical markers in a wastewater sample allows back-calculating the amount of alcohol and tobacco consumed by the people contributing to that sample. This approach, also known as wastewater-based epidemiology (WBE), provides information on substance abuse in a rapid, anonymous and objective way, complementing the information obtained by traditional methods (surveys, medical and criminal indices, etc). WBE has been used in Spain to estimate the consumption of legal and illicit psychoactive substances. While 4 Spanish cities systematically apply the WBE on an annual basis to report the use of illicit drugs to the European Monitoring Centre for Drugs and Drugs Addiction, the WBE has been only occasionally applied in few cities to estimate alcohol and tobacco use. Based on this, the present work aimed at extending the application of the WBE approach in the Spanish territory (14 cities, 17 WWTPs, 13% of the Spanish population) to obtain a more reliable picture on alcohol and tobacco consumption in the country. This work also aimed at evaluating spatial and weekly consumption trends of these legal drugs and compare WBE-derived data with official consumption figures. For this, 24-h composite wastewater samples were collected at the inlet of 17 wastewater treatment plants (WWTPs) during one week in spring 2018, covering approximately 13% of the Spanish population, and urban areas of different size. The samples collected were analysed for urinary biomarkers of alcohol and nicotine (main psychoactive substance of tobacco). Results showed the presence of the three metabolites in all samples analyzed. Spatial variations in alcohol and nicotine consumption were observed among the investigated cities, and in the case of alcohol, also different consumption patterns were observed during the week. Extrapolation of WBE-derived consumption data at national level showed an annual consumption of alcohol lower than that reported by the World Health Organization (WHO). However, in the case of nicotine, consumption obtained by WBE approach was very similar to tobacco., This work has been supported by the Spanish State Research Agency (Agencia Estatal de Investigación, AEI) through the “Redes de Excelencia” programme, ESAR-Net, ref. CTM2016-81935-REDT

Resumen del trabajo presentado en el SETAC Europe 30th Annual Meeting, celebrado en modalidad virtual del 3 al 7 de mayo de 2020., Data obtained from wastewater analysis can provide rapid and complementary insights in illict drug consumption at community level. Drug use has been assessed through wastewater analysis at national level in, for example, Australia, Belgium, Finland and South Korea and has also provided annually a one week snapshot of illicit drug volumes consumed in European cities (http://www.emcdda.europa.eu/topics/ pods/waste-water-analysis). However, a wastewater monitoring program did not exist in Spain, but leading experts have formed a network (https://www.esarnet.es/) to promote wastewater-based epidemiology at national level and communicate their findings to authorities and policymakers. Within Europe, Spain is an important country of transit of both cocaine and cannabis, due to its cultural, linguistic and colonial ties to Latin America and its proximity to Morocco. The quantity of seized cocaine and cannabis and prevalence of use, locates Spain at the top of Europe. In this work, a national wastewater campaign has been performed to get more insight on the consumption of illicit drugs and NPS within Spain for the first time. Wastewater results from 14 Spanish cities were compared with previously reported data and other national indicators. The cities, located in 7 of the 17 autonomous communities, 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 to these conventional drugs, weekend samples were monitored for several new psychoactive substances (NPS) (i.e. phenethylamines and cathinones). The selected NPS are known as possible replacement of these conventional drugs or among those previously reported. Finally, enantiomeric profiling of amphetamine was performed for one city in order to assure the results were due to consumption and not illegal dumping of production residues. This demonstrates another application of wastewater-based epidemiology, which allows to identify the originof drugs in wastewater., This work has been supported by the Spanish State Research Agency (Agencia Estatal de Investigación, AEI) through the “Redes de Excelencia” programme, ESAR-Net, ref. CTM2016-81935-REDT

Many inland waters exhibit complete or partial desiccation, or have vanished due to global change, exposing sediments to the atmosphere. Yet, data on carbon dioxide (CO 2) emissions from these sediments are too scarce to upscale emissions for global estimates or to understand their fundamental drivers. Here, we present the results of a global survey cov- ering 196 dry inland waters across diverse ecosystem types and climate zones. We show that their CO 2 emissions share fundamental drivers and constitute a substantial fraction of the carbon cycled by inland waters. CO2 emissions were consistent across ecosystem types and climate zones, with local characteristics explaining much of the variability. Accounting for such emissions increases global estimates of carbon emissions from inland waters by 6% (~0.12 Pg C y−1). Our results indicate that emissions from dry inland waters represent a significant and likely increasing component of the inland waters carbon cycle. This study was made possible thanks to a large collective effort of a global research network called dryflux (www.ufz.de/dryflux). We would like to thank numerous helpers for their assistance during field work. This research was inspired by GLEON (Global Lake Ecological Observatory Network). This work was supported by the German Research Foundation (DFG, KO1911/6-1 and GR1540/23-1) to P.S.K. and H.P.G., the Spanish Ministry of Science, Innovation and Universities (C-HYDROCHANGE, CGL2017-86788-C3-3-P and CGL2017-86788-C3-2-P) to B.O. and R.M., the Spanish Government (CGL2016-77487-R), the Basque Government (IT951-16), the BBVA Foundation (06417) to D.vS. and A.E., the European Research Council (FP7/2007-2013, ERC grant agreement 336642) to A.L. and R.F.M., CNPq (310033/2017-9) to A.M.A., the Carlsberg Foundation (CF16-0325) to T.R. and A.P., the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO, Veni Grant 86312012) to S.K., the Estonian Ministry of Education and Research (IUT 21-02) and the Estonian Research Council grant (PUT PSG32, PUT1598) to A.L. and E-I.R., the National Research Foundation of Korea (2017R1D1A1B06035179) to J-H.P., German Federal Ministry of Education and Research (BMBF) CLIENT programme (grant: 2WCL1337A) and German Academic Exchange Service (DAAD, grant 57218695) to M.A.F., the Seneca Foundation (20645/ JLI/18) to M.M.S.M. and M.I.A. N.C. was supported by Beatriu de Pinós grant (2016- 00215), A.P. by the Ramón Areces Foundation postgraduate studies programme, R.dC. by the University of Murcia (FPU R-269/2014), E.S.O.J. by the Erasmus+ Programme NON-EU 2017/2018, J.R.P. by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES Finance Code 001). C.M-L. by the French Agency for Biodiversity (ONEMA-AFB, Action 13, ‘Colmatage, échange snappe-rivière et processus biogéochi- miques’), R.M. by the project C-HydroChange, funded by the Spanish Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER) under the contract FEDER-MCIU-AEI/ CGL2017-86788-C3, P.S.K. by a grant for a short‐term scientific mission within the COST Action CA15113 (SMIRES, Science and Management of Intermittent Rivers and Ephemeral Streams, www.smires.eu) and GLEON (student travel grant). In memory of our esteemed colleague and friend Julia Howitt, who passed away after this paper was accepted. She was full of enthusiasm for this work and will be deeply missed by her colleagues around the world. This study was made possible thanks to a large collective effort of a global research network called dryflux (www.ufz.de/dryflux). We would like to thank numerous helpers for their assistance during field work. This research was inspired by GLEON (Global Lake Ecological Observatory Network). This work was supported by the German Research Foundation (DFG, KO1911/6-1 and GR1540/23-1) to P.S.K. and H.P.G., the Spanish Ministry of Science, Innovation and Universities (C-HYDROCHANGE, CGL2017-86788-C3-3-P and CGL2017-86788-C3-2-P) to B.O. and R.M., the Spanish Government (CGL2016-77487-R), the Basque Government (IT951-16), the BBVA Foundation (06417) to D.vS. and A.E., the European Research Council (FP7/2007-2013, ERC grant agreement 336642) to A.L. and R.F.M., CNPq (310033/2017-9) to A.M.A., the Carlsberg Foundation (CF16-0325) to T.R. and A.P., the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO, Veni Grant 86312012) to S.K., the Estonian Ministry of Education and Research (IUT 21-02) and the Estonian Research Council grant (PUT PSG32, PUT1598) to A.L. and E-I.R., the National Research Foundation of Korea (2017R1D1A1B06035179) to J-H.P., German Federal Ministry of Education and Research (BMBF) CLIENT programme (grant: 2WCL1337A) and German Academic Exchange Service (DAAD, grant 57218695) to M.A.F., the Seneca Foundation (20645/ JLI/18) to M.M.S.M. and M.I.A. N.C. was supported by Beatriu de Pinós grant (2016- 00215), A.P. by the Ramón Areces Foundation postgraduate studies programme, R.dC. by the University of Murcia (FPU R-269/2014), E.S.O.J. by the Erasmus+ Programme NON-EU 2017/2018, J.R.P. by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES Finance Code 001). C.M-L. by the French Agency for Biodiversity (ONEMA-AFB, Action 13, ‘Colmatage, échange snappe-rivière et processus biogéochi- miques’), R.M. by the project C-HydroChange, funded by the Spanish Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER) under the contract FEDER-MCIU-AEI/ CGL2017-86788-C3, P.S.K. by a grant for a short‐term scientific mission within the COST Action CA15113 (SMIRES, Science and Management of Intermittent Rivers and Ephemeral Streams, www.smires.eu) and GLEON (student travel grant). In memory of our esteemed colleague and friend Julia Howitt, who passed away after this paper was accepted. She was full of enthusiasm for this work and will be deeply missed by her colleagues around the world.

Intermittent rivers and ephemeral streams (IRES) encompass fluvial ecosystems that eventually stop flowing and run dry at some point in space and time. During the dry phase, channels of IRES consist mainly of dry riverbeds (DRBs), prevalent yet widely unexplored ecotones between dry and wet phases that can strongly influence the biogeochemistry of fluvial networks. DRBs are often overlooked because they do not strictly belong to either domain of soil or freshwater science. Due to this dual character of DRBs, we suggest that concepts and knowledge from soil science can be used to expand the understanding of IRES biogeochemistry. Based on this idea, we propose that DRBs can be conceptually understood as early stage soils exhibiting many similarities with soils through two main forces: i) time since last sediment transport event, and ii) the development status of stabilizing structures (e.g. soil crusts and/or vascular plants). Our analysis suggests that while DRBs and soils may differ in master physical attributes (e.g. soil horizons vs fluvial sedimentary facies), they become rapidly comparable in terms of microbial communities and biogeochemical processes. We further propose that drivers of DRBs biogeochemistry are similar to those of soils and, hence, concepts and methods used in soil science are transferable to DRBs research. Finally, our paper presents future research directions to advance the knowledge of DRBs and to understand their role in the biogeochemistry of intermittent fluvial networks. © 2018 The Authors This paper resulted from discussions conducted as part of working group 3 “Coupled Aquatic-terrestrial Biogeochemistry in IRES” based upon work from COST Action CA15113 (SMIRES, Science and Management of Intermittent rivers and Ephemeral streams; www.smires.eu ) supported by COST (European Cooperation in Science and Technology). Additional support was provided for MIA by an Alexander von Humboldt Grant (Ref: 1162886 ) and a Juan de la Cierva Grant (Ref: FJCI-2015-26192 ), for CM-L by an Early Career Fellowship from the Graduate Research School (GRS) at BTU Cottbus-Senftenberg and by the French Agency for Biodiversity (ONEMA-AFB, Action 13, Colmatage, échange snappe-rivière et processus biogéochimiques), for MA by the Spanish Government (Ref: DISECO CGL-2014-55-405-R ) and by a Juan de la Cierva Grant (Ref: IJCI-2015-23500 ), for NC by a Juan de la Cierva Grant (Ref: FJCI-2014-23064 ), for SB by Spanish Government (Ref: NICUS CGL-2014-55234-JIN ), for RG by the Science and Technology Agency of Murcia Region (SENECA Foundation, Ref: 19525/PI/14 ), for OS by the SMART joint Doctorate Programme (Science for the MAnagement of Rivers and their Tidal systems, funded by the Erasmus Mundus programme of the European Union ) and for DvS by the Spanish Government (Ref: CGL2016-77487-R ) and Basque Government (Ref: IT951-16 ).

Synthetic cathinones have become popular in recent years, which would explain why their determination in influent sewage samples has already been documented. In the present study a method based on solid-phase extraction followed by liquid chromatography and high resolution mass spectrometry is developed, validated and applied to determine twelve cathinones and one of their metabolites in different environmental samples including influent and effluent sewage and river water. Two cation-exchange sorbents (Oasis MCX and Oasis WCX) were compared, with better results achieved with Oasis WCX in terms of apparent recoveries (70–100%) and matrix effects (lower than −34%). The method was validated with effluent sewage samples providing suitable figures of merit, with method quantification limits ranging from 1 ng/L to 5 ng/L and method detection limits from 0.1 ng/L to 0.5 ng/L for all the compounds. Of the different cathinones studied, three, namely methylone, mephedrone metabolite and methylenedioxypyrovalerone, were quantified at concentration levels of low ng/L in each of the different samples analysed, while a number of the other cathinones were also detected in some of the samples.

11 pages, 6 figures, 3 tables, Currently, many water quality variables can be automatically monitored at subdaily frequencies, but most environmental datasets still rely heavily on comparatively low-frequency (e.g., monthly) sampling campaigns. Taking advantage of the long-term ecological data available from polymictic Lake Müggelsee (Germany) at weekly temporal scales, we tested whether dynamic factor analysis (DFA), a dimension-reduction technique especially designed for time series with data gaps, was able to reproduce the same underlying patterns if the resolution of the observations was artificially reduced from weekly to once every 2 or 4 weeks (2-weekly or 4-weekly, respectively) and whether the same results were obtained for different variables (water temperature, water chemistry, and plankton). As expected, the reduction in data resolution and the addition of gaps increased the amount of variance in our case studies; however, water temperature patterns, which generally vary only slowly if considered at broader temporal scales, were represented well in the 4-weekly data model. By contrast, total algal biomass and nutrient dynamics, which usually fluctuate more rapidly, were not. We further assessed the representativeness of spot samples taken by selection at 4-weekly and seasonal intervals compared to samples obtained by averaging the weekly data over these 2 intervals. In this case, the resulting observation variance was more pronounced in DFA models of the samples taken by selection than of those obtained by averaging. The introduction of additional artificial gaps in one univariate and one multivariate model decreased the amount of information that could be explained by the pattern(s) extracted by DFA. Overall, we found that a too low sampling frequency could be a limiting factor when studying interactions and responses to changing conditions in aquatic systems, particularly when biological variables are involved, R. Aguilera benefited from a Short-Term Scientific Mission at the Leibniz-Institute of Freshwater Ecology and Inland Fisheries, Berlin, funded by the ESSEM COST Action ES1201 NETLAKE (Networking Lake Observatories in Europe). D.M. Livingstone benefited from time spent as guest scientist at the Leibniz-Institute of Freshwater Ecology and Inland Fisheries, Berlin, funded by the IGB Fellowship Program in Freshwater Science. R. Adrian was supported through the German Science Foundation project LakeRisk (AD 91/13-1), European Cooperation in Science and Technology, Deutsche Forschungsgemeinschaft

A new sorptive extraction technique, fabric phase sorptive extraction (FPSE), using different coating chemistries: non-polar sol-gel poly(dimethyldiphenylsiloxane) (PDMDPS), medium polar sol-gel poly(tetrahydrofuran) (PTHF), and polar sol-gel poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG triblock) and sol-gel Carbowax 20M were evaluated to extract a group of pharmaceuticals and personal care products (PPCPs) with wide range of polarity from environmental aqueous samples. Different parameters affecting FPSE such as sample pH, stirring speed, addition of salt, extraction time, sample volume, elution solvent and desorption time were optimized for each sorbent coated FPSE media. Under optimum conditions, FPSE media coated with sol-gel Carbowax 20M provided the highest absolute recoveries (77-85%) for majority of the analytes with the exception of the most polar ones. Nevertheless, all four sorbents offered better recovery compared to the commercially available coating for stir-bar sorptive extraction based on Ethylene Glycol/Silicone (EG/Silicone). The method based on FPSE with sol-gel Carbowax 20M media and liquid chromatography–(electrospray ionization) tandem mass spectrometry (LC-(ESI) MS/MS) was developed and validated for environmental water samples. Good apparent recoveries (41 - 80%), detection limits (1 - 50 ng L-1), repeatability (%RSD

The aim of the present study is to broaden the applications of mixed-mode ion-exchange solid-phase extraction sorbents to extract both basic and acidic compounds simultaneously by combining the sorbents in a single cartridge and developing a simplified extraction procedure. Four different cartridges containing negative and positive charges in the same configuration were evaluated and compared to extract a group of basic, neutral, and acidic pharmaceuticals selected as model compounds. After a thorough optimization of the extraction conditions, the four different cartridges showed to be capable of retaining basic and acidic pharmaceuticals simultaneously through ionic interactions, allowing the introduction of a washing step with 15 mL methanol to eliminate interferences retained by hydrophobic interactions. Using the best combined cartridge, a method was developed, validated, and further applied to environmental waters to demonstrate that the method is promising for the extraction of basic and acidic compounds from very complex samples.

This work presents a new extraction material, namely, Q-100, based on hyper-crosslinked magnetic particles, which was tested in dispersive solid-phase extrac-tion for a group of sweeteners from environmental samples. The hypercrosslinkedQ-100 magnetic particles had the advantage of suitable pore size distribution andhigh surface area, and showed good retention behavior toward sweeteners. Differentdispersive solid-phase extraction parameters such as amount of magnetic particles orextraction time were optimized. Under optimum conditions, Q-100 showed suitableapparent recovery, ranging in the case of river water sample from 21 to 88% for allthe sweeteners, except for alitame (12%). The validated method based on dispersivesolid-phase extraction using Q-100 followed by liquid chromatography with tandemmass spectrometry provided good linearity and limits of quantification between 0.01and 0.1 μg/L. The method was applied to analyze samples from river water and efflu-ent wastewater, and four sweeteners (acesulfame, saccharin, cyclamate, and sucralose)were found in both types of sample.

This paper describes for the first time the use of a new extraction technique, based on fabric phase sorptive extraction (FPSE). This new mode proposes the extraction of the analytes in dynamic mode in order to reduce the extraction time. Dynamic fabric phase sorptive extraction (DFPSE) followed by liquid chromatography-tandem mass spectrometry was evaluated for the extraction of a group of pharmaceuticals and personal care products (PPCPs) from environmental water samples. Different parameters affecting the extraction were optimized and best conditions were achieved when 50mL of sample at pH 3 was passed through 3 disks and analytes retained were eluted with 10mL of ethyl acetate. The recoveries were higher than 60% for most of compounds with the exception of the most polar ones (between 8% and 38%). The analytical method was validated with environmental samples such as river water and effluent and influent wastewater, and good performance was obtained. The analysis of samples revealed the presence of some PPCPs at low ngL(-1) concentrations.

Synthetic cathinones have become popular in recent years, which would explain why their determination in influent sewage samples has already been documented. In the present study a method based on solid-phase extraction followed by liquid chromatography and high resolution mass spectrometry is developed, validated and applied to determine twelve cathinones and one of their metabolites in different environmental samples including influent and effluent sewage and river water. Two cation-exchange sorbents (Oasis MCX and Oasis WCX) were compared, with better results achieved with Oasis WCX in terms of apparent recoveries (70–100%) and matrix effects (lower than −34%). The method was validated with effluent sewage samples providing suitable figures of merit, with method quantification limits ranging from 1 ng/L to 5 ng/L and method detection limits from 0.1 ng/L to 0.5 ng/L for all the compounds. Of the different cathinones studied, three, namely methylone, mephedrone metabolite and methylenedioxypyrovalerone, were quantified at concentration levels of low ng/L in each of the different samples analysed, while a number of the other cathinones were also detected in some of the samples.