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In order to move forward in the acceptance of a novel contaminant monitoring technique (Diffusive Gradients in Thin-films: DGT) for assessment of marine water bodies, sensu the WFD, an Inter-Laboratories Comparison (ILC) exercise (nine Europeans laboratories) was organized in the framework of the Interreg Atlantic Area MONITOOL project, which focused on the use of the DGT technique for the measurement of WFD priority metals (Cd, Ni and Pb). Reproducible results were obtained for each metal by several laboratories, supporting the assertion that DGT analysis can be performed satisfactorily by laboratories experienced in measuring metals at trace levels in marine environments, even if they have limited practice in DGT analysis. According to the Z-score analysis, among the 9 participating laboratories, 3 had 100 % of satisfactory results for Cd, Ni, and Pb, 3 had >80 % satisfactory results and 2 had about 60 % satisfactory results. This work highlights the need to clearly describe the DGT method in order to control sources of contamination during analytical steps, in particular the resin gel retrieval and the elution steps. Such international intercomparison exercise is an important step to develop the laboratory network involved in DGT analysis and contributes to the improvement of data quality., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

The study of the presence of antibiotics in the aquatic environment is a preliminary step to analyse their possible harmful effects on aquatic ecosystems. In order to monitor their occurrence in the aquatic environment, the European Commission established in 2015, 2018, and 2020 three Watch Lists of substances for Union-wide monitoring (Decisions (EU) 2015/495, 2018/840, and 2020/1161), where some antibiotics within the classes of macrolides, fluoroquinolones and penicillins were included. In the Basque coast, northern Spain, three macrolide antibiotics (erythromycin, clarithromycin, azithromycin) and ciprofloxacin were monitored quarterly from 2017 to 2020 (covering a period before and after the COVID19 outbreak), in water samples collected from two Waste Water Treatment Plants (WWTPs), and three control points associated with receiving waters (transitional and coastal water bodies). This work was undertaken for the Basque Water Agency (URA). The three macrolide antibiotics in water showed a frequency of quantification >65 % in the Basque coast, with higher concentrations in the WWTP emission stations than in receiving waters. Their frequency of quantification decreased from 2017 to 2020, as did the consumption of antibiotics in Spanish primary care since 2015. Ciprofloxacin showed higher frequencies of quantification in receiving waters than in wastewaters, but the highest concentrations were observed in the WWTP emission stations. Although consumption of fluoroquinolones (among which is ciprofloxacin) in primary care in the Basque Country has decreased in recent years, this trend was not observed in the waters sampled in the present study. On the other hand, concentrations of clarithromycin, azithromycin, and ciprofloxacin in receiving waters exceeded their respective Predicted No-Effect Concentrations, so they could pose an environmental risk. These substances are widely used in human and animal medicine, so, although only ciprofloxacin is included in the third Watch List, it would be advisable to continue monitoring macrolides in the Basque coast as well., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Numerical models point to the south-east Bay of Biscay as a convergence area for floating particles, including plastics. The few existing studies on plastic abundance in the area mainly focus on open waters and yet information on the coastal area is limited. To fill this gap, neustonic samples were taken along the coastal waters of the south-east Bay of Biscay (2017-2020) to define the spatial distribution of plastic abundances and composition. Results show an average plastic abundance of 739,395 ± 2,625,271 items/km 2 (998 ± 4338 g/km 2 ). French waters were more affected, with five times higher plastic abundances than Spanish coasts. Microplastics represented 93 % of the total abundance of plastic items (28 % in weight), mesoplastics 7 % (26 %) and macroplastics 1 % (46 %). This study demonstrates that this area is a hotspot for plastic with levels in coastal waters similar to those in the Mediterranean Sea or other litter aggregation areas., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study investigates the relationships among Ni, Cd and Pb's different chemical forms determined by different methodologies in coastal and transitional waters across a broad geographical scale. Concentrations were measured in spot samples and through passive sampling (DGT). High variability of metal concentrations was found among sampling sites and methodologies due to natural water fluctuations rather than to a given metal or method. Total dissolved metal concentrations in spot samples were lower than the EQS-WFD values. The labile fractions of Cd and Pb, measured in spot samples by Anodic Stripping Voltammetry and by DGT-ICPMS, were highly correlated. Similar labilities were found for Cd, while for Pb, the ASV labile fraction was ≈50% lower. These results reflect the pool of mobile and labile species available towards each technique kinetic window, and they seem not to be affected by discrete sampling flaws., (Crown Copyright © 2022. Published by Elsevier Ltd. All rights reserved.)

Using a long-term (1995-2014) monitoring network, from 51 sampling stations in estuaries and coasts of the Basque Country (Bay of Biscay), the objective of this investigation was to assess the responsiveness of 83 variables in water (18), sediments (27), biota (26), phytoplankton (2), macroinvertebrates (5) and fishes (5) to different human pressures and management actions. We used a total of 3247 series of data to analyse trends of improvement and worsening in quality. In a high percentage of the cases, the management actions taken have resulted in positive effects in the environment, as shown by the trend analysis in this investigation. Overall, much more trends of improvement than of worsening have been observed; this is true for almost all the media and biological components studied, with the exception of phytoplankton; and it applies as well to almost all the stations and water bodies, with the exception of those corresponding to areas with water treatment pending of accomplishment. In estuaries with decreasing human pressures during the period, the percentage of series showing quality improvement was higher (approx. 30%) than those showing worsening of quality (12%). Moreover, in those water bodies showing an increase of pressure, variables which can be considered indicators of anthropogenic effects showed negative trends (quality worsening). On the other hand, some of the variables analysed were more affected by natural variability than by changes in pressures. That was the case of silicate, nitrate and suspended solids, which followed trends correlated to salinity, which, in turn, was related to the rainfall regime during the study period., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Liver and gonad histopathology, biometric parameters and hepatic metal bioaccumulation were assessed monthly over a one-year period in common soles from the Basque continental shelf, in order to determine baseline levels and confounding factors within biomonitoring studies. Biometric parameters and hepatic metal bioaccumulation varied according to season and gender. Accordingly, hepatic histopathological traits presented seasonal variations related to the reproductive cycle. However, the hepatic histopathological index showed that seasonality and gender were not significant confounding factors. Conversely, the gonad histopathological index was modulated by season and gender. As for organ comparison, the liver endured more severe histopathological damage than the gonad. In brief, the sampling period and gender may not affect the estimation of hepatic histopathological indices for biomonitoring purposes. Nonetheless, due to different sensitivities to environmental 'noise' variables, the sampling period and gender differentiation should be thoroughly considered for the assessment of gonad histopathology, biometrics and metal bioaccumulation., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Interannual variability of polychlorinated biphenyls (PCBs), measured in the soft tissues of Mytilus galloprovincialis mussels and Crassostrea gigas oysters, collected from estuarine waters within the Basque Country (Bay of Biscay), are investigated. Samples were collected in the autumn, between 2002 and 2011. Sites located within the ports of Bilbao and Pasaia showed the highest PCBs concentrations in molluscs; the lowest were observed in the mouth of the Oka estuary, an area of low population and industrial activity. Congener profiles of PCBs in the tissues of molluscs reveal the predominance of hexachlorobiphenyls (CB153 and CB138). In addition, redundancy analysis has shown that residence time, river flow and a 'pressure index' explain 57% of the variability in the PCB congener concentrations (the higher the values of these variables, the higher the concentration). Finally, Σ7PCB median concentrations in molluscs and sediments, collected from nearby sampling sites, were found to be moderately correlated (r(2)=0.513, p<0.01)., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

According to Water Framework Directive requirements, Member States must identify and analyze effects derived from human pressures in aquatic systems. As different kind of pressures can impact water bodies at different scales, analyses of spatio-temporal evolution of water bodies becomes essential in order to understand ecosystem responses. In this investigation, an analysis of spatio-temporal evolution of sedimentary metal pollution (Cd, Cr, Cu, Hg, Ni, Pb, Zn) in 12 Basque estuaries (Bay of Biscay) is presented. Data collected in extensive sampling surveys is the basis for the GIS-based statistical approach used. The implementation of pollution abatement measures is reflected in a long-term decontamination process, mostly evident in estuaries with highest historical sediment pollution levels. Spatial evolution is determined by either naturally occurring or human driven processes. Such spatial processes are more obviously being reflected in estuaries with lower historical sediment pollution levels., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

In this contribution, the potential use of diffusive gradients in thin-films (DGTs) for the chemical evaluation of transitional water bodies within the Water Framework Directive (WFD) has been studied. The water metal concentration has been evaluated in 13 estuaries in the southeastern Bay of Biscay. The DGTs were deployed in triplicate at two stations in each estuary, delimiting the tidal influence. The DGT results were in the ranges of 2-1570 ng L(-1) for cadmium, 66-515 ng L(-1) for copper, 30-3650 ng L(-1) for nickel and 0.8-95.5 μg L(-1) for zinc. The DGTs provided reliable average labile metal concentrations in highly dynamic systems that were comparable with DGT measurements in coastal and estuarine waters worldwide. In addition, it was possible to discriminate those estuaries more susceptible to environmental impacts, being consistent with the historical contamination of each estuary. Based on the obtained results, a sampling strategy for the monitoring of transitional water bodies using DGTs is proposed., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were measured in surficial sediments at, the ports of Pasaia and Bilbao, together with other mid- and small-size harbours of the Basque Country (northern Spain), in 2007-2008. The highest values of the sum of the three measured butyltin species (3523-3640 ng g(-1), as Sn) were found at sampling stations near to shipyards located within the port of Pasaia. The highest value of TBT concentration (3143 ng g(-1), as Sn) was found at the marina of Getxo, in the port of Bilbao. The degree of TBT degradation varied greatly between sampling stations, being found to be generally higher in those sediments with higher values of redox potential and lower values of TBT concentration (normalized by organic matter content)., (Copyright 2009 Elsevier Ltd. All rights reserved.)

The European Water Framework Directive (WFD) establishes a framework for the protection and improvement of estuarine (transitional) and coastal waters, attempting to achieve good water status by 2015; this includes, within the assessment, biological and chemical elements. The European Commission has proposed a list of priority dangerous substances (including metals such as Cd, Hg, Ni and Pb), with the corresponding list of environmental quality standards (EQS), to assess chemical status, but only for waters. In this contribution, a long-term (1995-2007) dataset of transitional and coastal water and sediment trace elements concentrations, from the Basque Country (northern Spain), has been used to investigate the response of these systems to water treatment programmes. Moreover, the approach proposed in the WFD, for assessing water chemical status (the 'one out, all out' approach), is compared with the integration of water and sediment data, into a unique assessment. For this exercise, background levels are used as reference conditions, identifying the boundary between high and good chemical status. EQS are used as the boundary between good and moderate chemical status. This contribution reveals that the first approach can lead to misclassification, with the second approach representing the pattern shown by the long-term data trends. Finally, the management implications, using each approach are discussed.