Metal concentrations in transitional and coastal waters measured by passive (Diffusive Gradients in Thin-films) and spot sampling: MONITOOL Project Dataset.

The MONITOOL project (2017-2023) was carried out to describe the relationships between total dissolved and labile metal concentrations measured in spot water samples and in concurrently deployed Diffusive Gradients in Thin-films (DGTs) passive samplers, respectively. The ultimate aim was to adapt existing marine metal Environmental Quality Standards (EQS marine water) for DGTs, enabling their use in the context of the European Directives (the Water Framework Directive (WFD) and the Marine Strategy Framework Directive (MSFD)). Time-integrated metal concentrations provided by DGTs, representing several days, are an advantage compared to conventional spot sampling, especially in highly dynamic systems, such as transitional waters. Hence, the MONITOOL project aimed to provide a robust database of dissolved and labile metal concentrations in transitional and coastal waters, based upon co-deployments of DGTs and collection of spot water samples at several sampling sites (England, France, Ireland, Italy, Northern Ireland, Portugal, Scotland and Spain), followed subsequently by DGT and water metal analysis. Samplings were carried out in 2018 and 2022, following agreed protocols developed in the framework of the project. The MONITOOL dataset includes metal concentrations from DGTs, measured with Inductively Coupled Plasma Mass Spectrometry (ICP-MS: Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) and in concurrently collected spot water samples by ICP-MS (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and Anodic/Cathodic Stripping Voltammetry (ASV/CSV: Cd, Pb, Ni). Moreover, data on seawater physical-chemical parameters (salinity, temperature, dissolved oxygen, pH, turbidity, total suspended solids, dissolved organic carbon, and total organic carbon) is provided. This database presents the results obtained using, concurrently, different forms of sampling and analytical techniques, enabling the comparison of the results obtained by these strategies and allowing the adaptation of EQS in marine water (EQS marine water) to DGTs (EQS DGT), in the context of the WFD. Moreover, due to the large number of sampling sites, it could also be used for other types of research, such as those dealing with metal speciation or the determination of baseline levels.

Time series data (2008-2023) of polychlorinated dibenzo-p-dioxins, dibenzofurans and polychlorinated biphenyls in bivalves from Shellfish Production Areas of the Basque coast (SE Bay of Biscay).

The accumulation of contaminants in aquatic organisms is of concern to human health due to the potential for exposure through the consumption of seafood. This dataset presents the levels of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (DL-PCBs) (PCB-81, PCB-77, PCB-126, PCB-169, PCB-123, PCB-118, PCB-114, PCB-105, PCB-167, PCB-156, PCB-157 and PCB-189) in bivalves collected annually between 2008 and 2023 from the four Shellfish Production Areas of the Basque coast (southeastern Bay of Biscay). Additionally, data on 6 non-dioxin like polychlorinated biphenyls (NDL-PCBs) (PCB-28, PCB-52, PCB-101, PCB-153, PCB-138 and PCB-180) is provided for the 2012-2023 time period. Depending on the availability of bivalves at each Shellfish Production Area, different species, such as mussels (Mytilus galloprovincialis) and oysters (Magallana gigas and Ostrea edulis) were used for the evaluation. Bivalve samples were analyzed at the accredited Laboratory of Dioxins of the Institute of Environmental Assessment and Water Research - CSIC in Spain, following standardized methodologies according to the specific requirements established at the corresponding EU Regulation. Concentrations and the World Health Organization-Toxic Equivalents (WHO-TEQ) were calculated. Considering the data from the four Shellfish Production Areas and the study period, WHO-TEQ values ranged from 0.12 to 0.64 pg g-1 wet weight for PCDD/Fs and from 0.45 to 2.23 pg g-1 wet weight for DL-PCBs, whereas concentrations ranged from 7.45 to 51.10 ng g-1 wet weight for NDL-PCBs. This database is useful for (i) assessing the spatial and temporal trends of PCDD/Fs and various PCBs in bivalves from the Basque coast, (ii) determining the relative contribution of different congeners, (iii) comparison with levels for human consumption and environmental quality standards, as well as with levels of other biogeographical areas, and (iv) the management of Shellfish Production Areas on the Basque coast.

Data on growth performance and survival of black scallops (Mimachlamys varia (Linnaeus, 1758)) reared under suspended conditions in waters of the Basque coast (SE Bay of Biscay).

This dataset presents the growth performance and survival of black scallops (Mimachlamys varia) reared under suspended conditions using different growing systems at two different sites of the Basque coast (SE Bay of Biscay). Monthly data on environmental variables (temperature, salinity, oxygen saturation and chlorophyll "a" concentration) in the water column is also provided. Juveniles obtained from a hatchery with a mean length of 23.6 ± 4.12 mm and a mean wet weight of 2.06 ± 1.09 g were deployed in cages and pots at two experimental sites: a raft installed in sheltered waters and a longline located at offshore waters. The experiment was run from June 2019 to August 2020 (447 days). Black scallops were collected every one or two months and at each sampling time a cage and a pot were retrieved from each site. Black scallop survival and growth performance were determined. This database is useful for (i) assessing the viability of the species on the Basque coast, (ii) determining the time needed for black scallops to reach commercial size, (iii) promoting species diversification in the emerging offshore aquaculture sector in the Basque Country and, (iv) for comparison with other biogeographical areas.

An international intercomparison exercise on passive samplers (DGT) for monitoring metals in marine waters under a regulatory context.

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.

Antibiotics in the Basque coast (N Spain): Occurrence in waste and receiving waters, and risk assessment (2017-2020).

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.

Metals concentrations in transitional and coastal waters by ICPMS and voltammetry analysis of spot samples and passive samplers (DGT).

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.

Dataset of macrobenthic species, organic matter content and grain-size distribution in surficial seafloor sediments in outer continental shelf, pockmark fields and Capbreton Canyon tributaries in the southeastern Bay of Biscay.

This dataset presents the macrobenthic species abundance and biomass in soft bottom areas located at southeastern Bay of Biscay. Data on organic matter content and grain-size distribution in surficial seafloor sediments is also provided. Samples were obtained with Shipek and Smith-McIntyre type grabs in several surveys carried out between 2010 and 2020, covering a range of depths of 32-2241 m. Abundance and biomass of macrobenthic species are given. This database is useful for (i) research on spatial variability of macrobenthic communities, and (ii) baseline knowledge of species in the area. The research article on these data [1] was published in the journal Regional Studies in Marine Science. Title: Macrofaunal variability in the continental shelf and canyons in the southeastern Bay of Biscay.

Concurrent sampling of transitional and coastal waters by Diffusive Gradient in Thin-films (DGT) and spot sampling for trace metals analysis.

This protocol was developed based on the knowledge acquired in the framework of the Interreg MONITOOL project (EAPA_565/2016) where extensive sampling campaigns were performed in transitional and coastal waters covering eight European countries. It provides detailed procedures and guidelines for the sampling of these waterbodies by concurrent collection of discrete water samples and the deployment of Diffusive Gradient in Thin-films (DGT) passive samplers for the measurement of trace metal concentrations. In order to facilitate the application of this protocol by end-users, it presents steps to follow in the laboratory prior to sampling campaigns, explains the procedures for field campaigns (including in situ measurement of supporting parameters) and subsequent sample processing in the laboratory in preparation for trace metal analyze by inductively coupled plasma-mass spectrometry (ICP-MS) and voltammetry. The protocol provides a systematic, coherent field sampling and sample preparation strategy that was developed in order to ensure comparability and reproducibility of the data obtained from each project Partner in different regions. • Standardization of the concurrent sampling of transitional and coastal waters by DGT passive samplers and spot sampling. • Robust procedures and tips based on existing international standards and comprehensive practical experience. • Links to demonstration videos produced within the MONITOOL project.

Assessing variability in the ratio of metal concentrations measured by DGT-type passive samplers and spot sampling in European seawaters.

The current study evaluates the effect of seawater physico-chemical characteristics on the relationship between the concentration of metals measured by Diffusive Gradients in Thin films (DGT) passive samplers (i.e., DGT-labile concentration) and the concentrations measured in discrete water samples. Accordingly, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to measure the total dissolved metal concentrations in the discrete water samples and the labile metal concentrations obtained by DGT samplers; additionally, lead and cadmium conditional labile fractions were determined by Anodic Stripping Voltammetry (ASV) and total dissolved nickel was measured by Cathodic Stripping Voltammetry (CSV). It can be concluded that, in general, the median ratios of DGT/ICP and DGT/ASV(CSV) were lower than 1, except for Ni (median ratio close to 1) and Zn (higher than 1). This indicates the importance of speciation and time-integrated concentrations measured using passive sampling techniques, which is in line with the WFD suggestions for improving the chemical assessment of waterbodies. It is the variability in metal content in waters rather than environmental conditions to which the variability of the ratios can be attributed. The ratios were not significantly affected by the temperature, salinity, pH, oxygen, DOC or SPM, giving a great confidence for all the techniques used. Within a regulatory context such as the EU Water Framework Directive this is a great advantage, since the simplicity of not needing to use corrections to minimize the effects of environmental variables could help in implementing DGTs within monitoring networks.

Contaminants of emerging concern in the Basque coast (N Spain): Occurrence and risk assessment for a better monitoring and management decisions.

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%), 17ß-estradiol (E2) (9%), clarithromycin (7%), ciprofloxacin (7%), and diclofenac (5%); and therefore, their levels could pose an environmental risk.

Source characterization and spatio-temporal evolution of the metal pollution in the sediments of the Basque estuaries (Bay of Biscay).

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.