Search

The presence of pollutants in estuary and oceanic systems is a global problem and a serious concern to human and environmental health. Usually, environmental monitoring studies consider classical persistent organic pollutants (POPs). However, the lists of POPs keep continuously growing and new POPs and other emerging pollutants should be considered in new monitoring programs. So, this study aimed to investigate the distribution and profile of classical POPs (polychlorinated biphenyl (PCBs), organochlorine pesticides (OCPs), and polycyclic aromatic hydrocarbons (PAHs)), new POPs and emerging pollutants (polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), novel halogenated flame retardants (NFRs) and UV filters) in bivalve mollusc samples (both raft-cultivated and wild mussel, Mytilus galloprovincialis; cockle, Cerestoderma edule; and clam, Ruditapes descussatus) collected in nine Galician Rias during the period February 2012 to February 2013. A predominance of PAHs (6.8–317 ng/g dry weight (dw)) followed by PCBs (0.47–261 ng/g dw), UV filters (1.4–157 ng/g dw), PFCs (0.53–62 ng/g dw), OCPs (0.07–29 ng/g dw), PBDEs (0.31–6.6 ng/g dw) and NFRs (0.07–3.2 ng/g dw) was found in the studied bivalves, being the UV filter octocrylene the compound found at the highest concentration (141 ng/g dw in a cockle sample), while the PAHs chrysene and benzo(b)fluoranthene were the compounds with the highest average concentration (20 and 14 ng/g dw, respectively). Inter-species, temporal and geographical variations on pollutants concentration were assessed by multifactorial analysis of variance. Statistically significant differences among the type of mollusc were observed for levels of organochlorinated and organobrominated pollutants considered (PCBs, OCPs and PBDEs), which were detected at higher concentrations in wild mussel. On the other hand, the main PFCs and UV filters showed a higher detection frequency in cockle samples. Location played significant role for PAHs, PCBs and the main PBDEs, being the most polluted rias those more industrialized and populated, i.e. A Coruña, Ferrol and/or Vigo. Finally, sampling timepoint was also a significant factor for most of the families considered but with different profiles. Thus, PAHs and PCBs showed higher concentrations in both February 2012 and 2013 and lower in August 2012, while the main PBDEs were measured at higher concentrations in November 2012 and lower in February 2012; and the main NFRs, PFCs and UV filters were present at lower levels in February 2013 The authors acknowledge the financial support provided by Galician Government (Conselleria de Economía e Industria, Xunta de Galicia) in the framework of Projects 10MDS700006PR and ED431C2017/36 and by the Spanish Government through the Research Projects CTM2014-56628-C3-2-R, CTM2017-84763-C3-2-R and FEDER funds SI

Supercritical fluid chromatography (SFC), combined with mass spectrometry (MS), was employed for the determination of five chiral fungicides, from two different chemical families (acylalanine and triazol) in wine and vineyard soils. The effect of different SFC parameters (stationary phase, chiral selector, mobile phase modifier and additive) in the resolution between enantiomers and in the efficiency of compounds ionization at the electrospray source (ESI) was thorougly described. Under final working conditions, chiral separations of selected fungicides were achieved using two different SFC-MS methods, with an analysis time of 10 min and resolution factors from 1.05 to 2.45 between enantiomers. In combination with solid-phase extraction and pressurized liquid extraction, they permitted the enantiomeric determination of target compounds in wine and vineyard soils with limits of quantification in the low ppb range (between 0.5 and 2.5 ng mL−1, and from 1.3 to 6.5 ng g−1, for wine and soil, respectively), and overall recoveries above 80%, calculated using solvent-based standards. For azolic fungicides (tebuconazole, myclobutanil and penconazole) soil dissipation and transfer from vines to wines were non-enantioselective processes. Data obtained for acylalanine compounds confirmed the application of metalaxyl (MET) to vines as racemate and as the R-enantiomer. The enantiomeric fractions (MET-S/(MET-S+MET-R)) of this fungicide in vineyard soils varied from 0.01 to 0.96; moreover, laboratory degradation experiments showed that the relative dissipation rates of MET enantiomers varied depending on the type of soil L.P.M acknowledges a FPU grant to the Spanish Ministry of Science. This study was supported by Xunta de Galicia and Spanish Government through grants GRC-ED431C 2017/36, PGC2018-094613-B-I00, both co-funded by the EU FEDER program SI

Plasticizers are chemical compounds used in the production of flexible plastics for a large variety of applications. They are present in most of the environments and, hence, we are highly exposed to them via several routes (ingestion, inhalation, etc). Due to the endocrine disruption potential of some of these chemicals and the unknown toxicological effects of their alternatives, assessing human exposure to these contaminants is an issue of emerging concern. Herein we propose an analytical methodology for the determination of several plasticizer metabolites in wastewater as a non-invasive, cheap, and fast exposure monitoring tool complementary to the analysis of urine. A solid-phase extraction procedure followed by an ultra(high)-performance liquid chromatography-tandem mass spectrometry method was optimized and validated for 21 analytes among phthalate, terephthalate, and di-iso-nonyl cyclohexane-1,2-dicarboxylate metabolites. Method quantification limits ranged from 0.079 to 4.4 ng L−1. The method was applied to the analysis of seven daily composite wastewater samples collected in the NW of Spain. Metabolites of low molecular weight phthalates and of di-2-ethylhexyl phthalate were quantified in all samples, despite the existing regulations limiting the use of phthalates. Metabolites of terephthalates, introduced at the end of the 20th century as phthalate substituents, were also quantified in all samples, being the first time that they were detected in this matrix. Exposure back-calculation highlighted di-2-ethylhexyl terephthalate as the second most common plastic additive after diethyl phthalate in the population considered, reflecting the increasing substitution of di-2-ethylhexyl phthalate by its analogous terephthalate This work was financially supported by Agencia Estatal de Investigación, Spain (project no. CTM2017-84763-C3-2-R), Galician Council of Culture, Education and Universities, Spain (IGM postdoctoral contract, Plan Galego I2C-Modalidade B, grant no. ED481D-2017/003, AED predoctoral contract, grant no. ED481A-2020/258, and project no. ED431C-2017/36), Gil Dávila Foundation (AED research grant), and FEDER/ERDF 2022-11-26 SI

Sludge from sewage treatment plants (STPs) is recognized as a sink of moderate to high lipophilic compounds resistant to biodegradation. Herein, we investigate the presence of emerging pollutants in sewage sludge combining the information provided by mass spectrometry detection, following ultra-performance liquid chromatography (UPLC), with the use of an accurate spectral database of pesticides and pharmaceuticals. In a first step, the performance of matrix solid-phase dispersion, as sample preparation technique, and two non-target data acquisition strategies (data dependent, DDA, and data independent analysis modes, DIA), used in combination with a UPLC quadrupole time-of-flight system, are assessed using a selection of deuterated compounds added either to freeze-dried sludge samples, or to sludge extracts. Possibilities and limitations of both modes are discussed. Following the DDA approach, a group of 68 micropollutants was identified in sludge from different STPs. Some of them are reported in this compartment for the first time. Finally, semi-quantitative concentration data are reported for a group of 37 pollutants in samples obtained from 16 STPs. Out of them, 10 pharmaceuticals, showing detection frequencies and median sludge residues above 50% and 100 ng g−1, respectively; are highlighted as pollutants to be monitored in sludge in order to understand their behaviour during the wastewater treatment This study was supported by Xunta de Galicia and Spanish Government through grants GRC-ED431C 2017/36, PGC2018-094613-B-I00, both co-funded by the EU FEDER program SI

Plastics accumulation in marine ecosystems has notable ecological implications due to their long persistence, potential ecotoxicity, and ability to adsorb other pollutants or act as vectors of pathogens. The present work aimed to evaluate the physiological response of the gilthead seabream (Sparus aurata) fed for 90 days with a diet enriched with virgin and seawater exposed low-density polyethylene microplastics (LDPE-MPs) (size between 100 and 500 μM), followed by 30 days of depuration, applying oxidative stress and inflammatory markers in liver homogenates. No effects of LDPE-MPs treatments on fish growth were observed throughout this study. A progressive increase in antioxidant enzyme activities was observed throughout the study in both treatments, although this increase was higher in the group treated with seawater exposedMPs. This increase was significantly higher in catalase (CAT), glutathione reductase (GRd), and glutathione-s-transferase (GST) in the seawater exposedMPs group, with respect to the virgin group. In contrast, no significant differenceswere recorded in superoxide dismutase (SOD) and glutathione peroxidase (GPx) between both groups. Exposure to MPs also caused an increase in the oxidative damage markers (malondialdehyde and carbonyls groups). Myeloperoxidase activity significantly increased because of MPs treatments. After 30 days of depuration, antioxidant, inflammatory enzyme activities and oxidative damage markers returned to values similar to those observed in the control, SI

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.

15 pages, 6 figures, 3 tables, Organophosphate flame retardants (OPFRs) are (re-)emergent environmental pollutants increasingly being used because of the restriction of other flame retardants. The chlorinated OPFR, tris(1,3-dichloro-2-propyl) phosphate (TDCPP) is among those of highest environmental concern, but its potential effects in the marine environment have rarely been investigated. We exposed a widely used sentinel marine mussel species, Mytilus galloprovincialis, to 10 μg L−1 of TDCPP during 28 days and studied: (i) the kinetics of bioaccumulation and elimination of the compound, (ii) the effect on two molecular biomarkers, glutathione S-transferase (GST) and acetylcholinesterase (AChE) activities, and (iii) proteomic alterations in the gills, following an isobaric labeling quantitative shotgun proteomic approach, at two exposure times (7 and 28 days). Uptake and elimination of TDCPP by mussels were very fast, and the bioconcentration factor of this compound in mussels was 147 L kgww-1, confirming that this compound is not very bioaccumulative, as predicted by its chemical properties. GST activity was not affected by TDCPP exposure, but AChE activity was inhibited by TDCPP at both 7 and 28 days of exposure. Proteomic analysis revealed subtle effects of TDCPP in mussel gills, since few proteins (less than 2 % of the analysed proteome) were significantly affected by TDCPP, and effect sizes were low. The most relevant effects detected were the up-regulation of epimerase family protein SDR39U1, an enzyme that could be involved in detoxification processes, at both exposure times, and the down-regulation of receptor-type tyrosine-protein phosphatase N2-like (PTPRN2) after 7 days of exposure, which is involved in neurotransmitter secretion and might be related to the neurotoxicity described for this compound. Exposure time rather than TDCPP exposure was the most important driver of protein abundance changes, with 33 % of the proteome being affected by this factor, suggesting that stress caused by laboratory conditions could be an important confounding factor that needs to be controlled in similar ecotoxicology studies. Proteomic data are available via ProteomeXchange with identifier PXD019720, L.E. F.-G. is supported with a predoctoral fellowship from Xunta de Galicia (Consellería de Cultura, Educación e Ordenación Universitaria grant ED481A-2017/298) partially co-founded by operative program FSE Galicia 2014-2020. M.C. is supported by the Ramón y Cajal contract (Ministry of Science and Innovation of Spain). This study was funded by Xunta de Galicia (refs. ED431C 2017/36, ED431C 2017/46, ED431C 2020/05 and IN607B 2018/10) and the Spanish Agencia Estatal de Investigación (refs. CTM2017-84763-C3-R-2 and CTM2016-77945-C3), partially co-funded by the European Regional Development Fund (FEDER/ERDF)

The hypothesis that exposure to certain environmental chemicals during early life stages may disrupt reproduction across multiple non-exposed generations has significant implications for understanding disease etiology and adverse outcomes. We demonstrate here reproductive multi and transgenerational effects, at environmentally relevant levels, of one of the most prescribed human pharmaceuticals, simvastatin, in a keystone species, the amphipod Gammarus locusta. The transgenerational findings has major implications for hazard and risk assessment of pharmaceuticals and other contaminants of emerging concern given that transgenerational effects of environmental chemicals are not addressed in current hazard and risk assessment schemes. Considering that the mevalonate synthesis, one of the key metabolic pathways targeted by simvastatin, is highly conserved among metazoans, these results may also shed light on the potential transgenerational effects of simvastatin on other animals, including humans. This research was funded by COMPETE 2020, Portugal 2020, the European Union through the ERDF and the Portuguese Foundation for Science and Technology – FCT (Transobesogen project – Trans-phyletic obesogenic responses: from epigenetic modules to transgenerational environmental impacts, reference: PTDC/CTA-AMB/31544/2017 – NORTE-01-0145-FEDER-031544). This research was also supported by the National Funds through FCT under the projects (UIDB/04423/2020; UIDP/04423/2020), by the Spanish Agencia Estatal de Investigación (CTM2017-84763-C3-2-R), and by the Galician Council of Culture, Education and Universities (ED431C2017/36), cofounded by ERDF. A PhD grant awarded to Susana Barros (PD/BD/143090/2018) was funded by the FCT SI

Sediment samples (0–1 cm) and tube-dwelling polychaetes from the Norwegian Continental Shelf and the Barents Sea were collected, including areas close to oil and gas installations and remote locations. Microplastics (≥45 μm) were found in quantifiable levels in 27 of 35 sediment samples, from 0.039 to 3.4 particles/gdw (dw = dry weight); and in 9 of 10 pooled polychaete samples, from 11 to 880 particles/gww (ww = wet weight). Concentrations were significantly higher in tube-dwelling polychaetes than sediments from the same locations (p

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.

A novel approach based on the direct pulsed irradiation of UV-C light onto ibuprofen (IBP) solutions was evaluated in this work, as proof of concept for the direct removal of micropollutants. The experiments confirmed that laser irradiation is able to completely degrade IBP in 15 min in distilled water, with a DOC depletion of ca. 25% and with transformation products (TPs) remaining in solution and estimated to represent ca. 10% of the initial IBP concentration. In wastewater spiked samples, removal efficiency is slightly lower but still significant (ca. 5% IBP remaining after 15 min). Hence, this work suggests that low power solid state pulsed lasers, emitting at 266 nm wavelength, show promise for the removal of these type of micropollutants from water. These results open new opportunities towards the development of chemical-free water treatment methods based on direct, selective irradiation using state of the art, miniaturized laser devices., This research was partially supported by the Consellería de Educación Program for Development of a Strategic Grouping in Materials - AeMAT at the University of Santiago de Compostela under the Grant No. ED431E2018/08. C. Bao-Varela, B.J. Sieira, J.B. Quintana and R. Rodil also acknowledge Xunta de Galicia (ref. ED431B 2017/64, ref. ED431C2017/36) and Spanish Agencia Estatal de Investigación (CTM2017-84763-C3-R-2). Several of the above mentioned projects are cofounded by the European Regional Development Fund. G.F.F. & L.A.A. acknowledge support from Gobierno de Aragón “Construyendo Europa desde Aragón” (research group T54_20R).

An analytical method based on high-resolution quadrupole&ndash, time-of-flight (QToF) mass spectrometry has been developed as an alternative to the classical method, using a low-resolution ion trap (IT) analyzer to reduce interferences in N-nitrosamines determination. Extraction of the targeted compounds was performed by solid-phase extraction (SPE) following the United States Environmental Protection Agency (USEPA) -521 method. First, both electron impact (EI) and positive chemical ionization (PCI) using methane as ionization gas were compared, along with IT and QToF detection. Then, parameters such as limits of detection (LOD) and quantification (LOQ), linearity, and repeatability were assessed. The results showed that the QToF mass analyzer combined with PCI was the best system for the determination of the N-nitrosamines, with instrumental LOD and LOQ in the ranges of 0.2&ndash, 4 and 0.6&ndash, 11 ng mL&minus, 1, respectively, which translated into method LOD and LOQ in the ranges of 0.2&ndash, 1.3 and 0.6&ndash, 3.9 ng L&minus, 1, respectively. The analysis of real samples showed the presence of 6 of the N-nitrosamines in influent, effluent, and tap water. N-nitrosodimethylamine (NDMA) was quantified in all the analyzed samples at concentrations between 1 and 27 ng L&minus, 1. Moreover, four additional nitrosamines were found in tap and wastewater samples.

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 analyzed how maternal obesity affected fatty acids (FAs) in breast milk and their association with infant growth and cognition to raise awareness about the programming effect of maternal health and to promote a healthy prenatal weight. Mother&ndash, child pairs (n = 78) were grouped per maternal pre-pregnancy body mass index (BMI): normal-weight (BMI = 18.5&ndash, 24.99), overweight (BMI = 25&ndash, 29.99) and obese (BMI &gt, 30). Colostrum and mature milk FAs were determined. Infant anthropometry at 6, 18 and 36 months of age and cognition at 18 were analyzed. Mature milk exhibited lower arachidonic acid (AA) and docosahexaenoic acid (DHA), among others, than colostrum. Breast milk of non-normal weight mothers presented increased saturated FAs and n6:n3 ratio and decreased &alpha, linolenic acid (ALA), DHA and monounsaturated FAs. Infant BMI-for-age at 6 months of age was inversely associated with colostrum n6 (e.g., AA) and n3 (e.g., DHA) FAs and positively associated with n6:n3 ratio. Depending on the maternal weight, infant cognition was positively influenced by breast milk linoleic acid, n6 PUFAs, ALA, DHA and n3 LC-PUFAs, and negatively affected by n6:n3 ratio. In conclusion, this study shows that maternal pre-pregnancy BMI can influence breast milk FAs and infant growth and cognition, endorsing the importance of a healthy weight in future generations.

This is the Author’s Accepted Manuscript of the following article: Pérez-Mayán, L., Rodríguez, I., Ramil, M., Kabir, A., Furton, K., & Cela, R. (2019). Fabric phase sorptive extraction followed by ultra-performance liquid chromatography-tandem mass spectrometry for the determination of fungicides and insecticides in wine. Journal Of Chromatography A, 1584, 13-23. doi: 10.1016/j.chroma.2018.11.025 In this work, fabric phase sorptive extraction (FPSE) is investigated for the extraction and preconcentration of ultra-trace level residues of fungicides (19 compounds) and insecticides (3 species) in wine samples. Subsequently, the preconcentrated analytes are selectively determined using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Parameters affecting the efficiency and repeatability of the extraction are evaluated in depth; moreover, the proposed method is characterized in terms of linear response range, trueness, precision and limits of quantification (LOQs). The set-up of the extraction process and the type of coating were the variables exerting the most prominent effects in the repeatability and the yield of the extraction, respectively. Under optimized conditions, samples (10 mL of wine diluted with the same volume of ultrapure water) were extracted with a small amount of cellulose fabric (3 discs with 4 mm of diameter: total surface 0.38 cm2) coated with a sol-gel polyethylene glycol sorbent (sorbent amount 3.3 mg), immersed in the diluted sample, without being in direct contact with the PTFE covered magnetic stir bar. Following the overnight extraction step, analytes were quantitatively recovered using only 0.3 mL of an ACN-MeOH (80:20) mixture. Under equilibrium sampling conditions, the linear response range of the method varied from 0.2 to 200 ng mL−1, with limits of quantification (LOQs) between 0.03 and 0.3 ng mL−1. Relative recoveries ranged from 77 ± 6% to 118 ± 4%, and from 87 ± 4% to 121 ± 6% for red and white wines, respectively. Application of the optimized method to commercial wines demonstrated the existence of up to 9 out of 22 investigated compounds in the same wine sample. The compound identified at the highest concentration was iprovalicarb (IPR), with a value of 130 ± 9 ng mL−1 in a commercial white wine This study has been supported by the Spanish Government, Xunta de Galicia and E.U. FEDER funds (projects CTQ2015-68660-P and GRC-ED431C). L.P-M acknowledges a FPU contract to the Spanish Ministry of Education SI

This is the postprint (accepted manuscript) version of the article published by Taylor & Francis in the International Journal of Environmental Analytical Chemistry on December, 10th 2018. Available on-line: http://www.tandfonline.com//10.1080/03067319.2018.1554743 The levels of cocaine (COC) and its metabolites benzoylecgonine (BE) and cocaethylene (COE) in wastewater samples from Brasilia, Brazil, were determined using liquid chromatography coupled to hybrid quadrupole-time-of-flight mass spectrometry. The former metabolite was used to estimate cocaine consumption using a country-tuned correction factor that considers BE excretion rates for different routes of administration as well as the fraction of crack users in Brazil. A day-to-day analysis during a week indicates higher cocaine use in weekends with peaks on Sunday in both southern (7385 ± 121 mg day−1 1000 inhab−1) and northern (3566 ± 171 mg day−1 1000 inhab−1) areas of Brasilia. A significant high cocaine use was also observed in the Carnival Day of 2018 (6229 ± 219 mg day−1 1000 inhab−1). COE/BE ratios were used to assess COC and alcohol co-consumption since COE is produced during the co-consumption of both substances. Higher ratios were also observed during the weekend. However, higher ratios on Saturdays rather than Sundays may be explained by the decrease of BE excretion during the co-consumption with alcohol, which may lead to an underestimation of the cocaine use estimates on Saturdays, as well as by different patterns of co-consumption by powder and crack users, where the latter usually drink lower amounts of alcohol. Our data suggest that only 3% of cocaine was seized by the local Technical Police during the study This work was supported by the Federal District Research Foundation under Grant [193.000.916/ 2015]; the Spanish Agencia Estatal de Investigación under Grant [CTM2017-84763-C3-2-R]; the Galician Council of Culture, Education and Universities under Grants [ED431C2017/36]; IGM postdoctoral contract, Plan Galego I2C-Modalidade B, ED481D 2017/003; and FEDER/ERDF SI

This is the Author’s Accepted Manuscript of the following article: González-Mariño, I., Castro, V., Montes, R., Rodil, R., Lores, A., Cela, R., & Quintana, J. (2018). Multi-residue determination of psychoactive pharmaceuticals, illicit drugs and related metabolites in wastewater by ultra-high performance liquid chromatography-tandem mass spectrometry. Journal Of Chromatography A, 1569, 91-100. doi: 10.1016/j.chroma.2018.07.045 © Elsevier 2018. This manuscript version is made available under the CC-BY-NC-ND 4.0 license This study presents a new multi-residue analytical method for the simultaneous determination of 38 psychoactive drugs (including benzodiazepines, antidepressants and drugs of abuse) and related metabolites in raw wastewater. Potential analyte losses during sample filtration and stability in wastewater were evaluated. Analyte losses, especially for 12 compounds, were observed during filtration, indicating a strong sorption onto the filter material. In order to overcome this effect, filtered water samples were combined with methanolic washes of the corresponding filters and the resulting solutions were solid-phase extracted on mixed-mode (reverse-phase plus cation-exchange) sorbents. Extracts were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry. Quantification was performed by the internal standard method with isotopic labeled analogs. Recovery percentages varied between 65% and 137%; method quantification limits ranged between 0.2 and 22 ng/L in ultrapure water and between 0.3 and 30 ng/L in wastewater for all the analytes but three (for which they were ∼60–80 ng/L). The analysis of 24 h-composite samples collected during one week in the city of Santiago de Compostela demonstrated the ubiquity of 31 analytes, which were positively quantified in all samples. The highest concentrations were found for some of the antidepressants, with mean and maximum levels exceeding, in some cases, the levels previously reported in literature. This fact could be related to the additional washing step of the filters using methanol, which allowed to desorb retained analytes highlighting the importance of this step during the sample preparation protocol SI

This study proposes the monitoring of phthalate metabolites in wastewater as a nonintrusive and economic alternative to urine analysis for estimating human exposure to phthalates. To this end, a solid-phase extraction–liquid chromatography–tandem mass spectrometry method was developed, allowing for the determination of eight phthalate metabolites in wastewater (limits of quantification between 0.5 and 32 ng L–1). The analysis of samples from the NW region of Spain showed that these substances occur in raw wastewater up to ca. 1.6 μg L–1 and in treated wastewater up to ca. 1 μg L–1. Concentrations in raw wastewater were converted into levels of exposure to six phthalate diesters. For two of them, these levels were always below the daily exposure thresholds recommended by the U.S. Environmental Protection Agency and the European Food Safety Authority. For the other four, however, estimates of exposure surpassed such a threshold (especially the toddler threshold) in some cases, highlighting the significance of the exposure to phthalates in children. Finally, concentrations in wastewater were also used to estimate metabolite concentrations in urine, providing a reasonable concordance between our results and the data obtained in two previous biomonitoring studies This work was financed by Spanish Ministry of Economy and Competitiveness (MINECO; project no. CTM2014-56628-C3-2-R), Xunta de Galicia (GRC2013-020 and IGM postdoctoral contract “Plan Galego de Investigación, Innovación e Crecemento 2011–2015”) and FEDER/ERDF SI

This is the peer reviewed version of the following article: Mallo, N. , DeFelipe, A. P., Folgueira, I. , Sueiro, R. A., Lamas, J. and Leiro, J. M. (2017), Combined antiparasitic and anti‐inflammatory effects of the natural polyphenol curcumin on turbot scuticociliatosis. J Fish Dis, 40: 205217. doi:10.1111/jfd.12503, which has been published in final form at https://doi.org/10.1111/jfd.12503. This article may be used for noncommercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions The histiophagous scuticociliate Philasterides dicentrarchi is the aetiological agent of scuticociliatosis, a parasitic disease of farmed turbot. Curcumin, a polyphenol from Curcuma longa (turmeric), is known to have antioxidant and anti-inflammatory properties. We investigated the in vitro effects of curcumin on the growth of P. dicentrarchi and on the production of pro-inflammatory cytokines in turbot leucocytes activated by parasite cysteine proteases. At 100 μm, curcumin had a cytotoxic effect and completely inhibited the growth of the parasite. At 50 μm, curcumin inhibited the protease activity of the parasite and expression of genes encoding two virulence-associated proteases: leishmanolysin-like peptidase and cathepsin L-like. At concentrations between 25 and 50 μm, curcumin inhibited the expression of S-adenosyl-L-homocysteine hydrolase, an enzyme involved in the biosynthesis of the amino acids methionine and cysteine. At 100 μm, curcumin inhibited the expression of the cytokines tumour necrosis factor-alpha (TNF-α) and interleukin-1 beta (IL-1β) produced in turbot leucocytes activated by parasite proteases. Results show that curcumin has a dual effect on scuticociliatosis: an antiparasitic effect on the catabolism and anabolism of ciliate proteins, and an anti-inflammatory effect that inhibits the production of proinflammatory cytokines in the host. The present findings suggest the potential usefulness of this polyphenol in treating scuticociliatosis This work was financially supported by the European Union’s Horizon 2020 research and innovation programme under grant agreement No. 634429 (PARAFISHCONTROL) and by the Ministerio de Economía y Competitividad (Spain) under grant agreement AGL2014-57125-R SI

ParaFishControl is coordinated by Spanish National Research Council (CSIC)., Scuticociliatosis is a severe disease in farmed flatfish. However, the causative agent is not always accurately identified. In this study, we identified two isolates of scuticociliates from an outbreak in cultured fine flounder Paralichthys adspersus. Scuticociliate identification was based on morphological data, examination of life stages and the use of molecular approaches. The isolates were compared with a strain of Philasterides dicentrachi from turbot Scophthalmus maximus and with a strain deposited in the American Type Culture Collection as Miamiensis avidus ATCC® 50180™. The use of morphological, biological and molecular methods enabled us to identify the isolates from the fine flouder as P. dicentrarchi. Comparison of P. dicentrachi isolates and M. avidus revealed some differences in the buccal apparatus. Unlike P. dicentrarchi, M. avidus has a life cycle with three forms: macrostomes (capable of feeding on P. dicentrarchi), microstomes and tomites. Additionally, we found differences in the 18S rRNA and α- and β-tubulin gene sequences, indicating that P. dicentrarchi and M. avidus are different species. We therefore reject the synonymy/conspecificity of the two taxa previously suggested. Finally, we suggest that a combination of morphological, biological, molecular (by multigene analysis) and serological techniques could improve the identification of scuticociliates parasites in fish., This study was financially supported by grant AGL2014-57125-R from the Ministerio de Economía y Competitividad (Spain), by grant GPC2014/069 from the Xunta de Galicia (Spain) and by PARAFISHCONTROL project. This project received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No. 634429.