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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 ) 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 to DGTs (EQS )

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.

In order to move forward in the acceptance of a novel contaminant monitoring technique for the status assessment of marine water bodies, sensu the Water Framework Directive (WFD), an Inter-Laboratories Comparison (ILC) exercise was organized by Ifremer in the framework of the MONITOOL project - New tools for monitoring the chemical status in transitional and coastal waters under the EU WFD. This ILC focused on the use of DGT technique for the measurement of WFD priority metals (Cd, Ni and Pb). The objectives of this ILC were to test the performance of laboratories when analysing DGTs and to identify the critical handling (resin gel retrieval and elution) and analytical steps when working with DGT samplers, to establish recommendations to prevent misleading results.

Le présent document fournit des instructions pour les meilleures pratiques relatives à l’utilisation des échantillonneurs passifs à Gradient de Diffusion en couche mince (DGT) pour l’échantillonnage des eaux de transition et côtières à des fins de surveillance de la qualité de l’eau. La méthodologie définie dans ce guide a été développée par le consortium du projet Interreg MONITOOL de l’Union européenne afin d’assurer la comparabilité et la reproductibilité des données obtenues par chaque partenaire du projet dans les différentes régions. Le guide fournit des informations pratiques et détaillées sur tous les aspects à prendre en considération avant le déploiement de ces dispositifs et lors des étapes essentielles après leur déploiement, extraction et trai - tement ultérieur des échantillons pour l’analyse des métaux traces. Bien qu’il ne s’agisse pas d’un protocole standard, ces lignes directrices abordent la nécessité d’une approche commune et l’intention de promouvoir les meilleures pratiques.

This document provides guidance on best practice for the use of Diffusive Gradient in Thin films (DGT) passive samplers devices in sampling of transitional and coastal waters for water quality monitoring. The methodology1 to be addressed in this guide was developed by the consortium of the European Union’s Interreg MONITOOL Project in order to ensure comparability and reproducibility of the data obtained from each project Partner in different regions. The guide provides practical and detailed information on all the aspects to be considered before the deployment of these devices and the essential steps for their deployment, retrieval and subsequent sample processing for the analysis of trace metals. Although it is not aimed as a standard protocol, these guidelines address the need for a common approach and the intention to promote best practice.

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.

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 analyse 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.

Trace metal concentrations in muscle and liver tissues from two offshore species of skate were examined. Concentrations of mercury in muscle of Leucoraja circularis (n = 20; 23–110.5 cm total length, 157–490 m water depth) and L. fullonica (n = 24; 28.5–100 cm total length, 130–426 m water depth) were 0.02–1.8 and 0.04–0.61 mg kg− 1, respectively. Concentrations of both As and Hg increased with total length. Only the largest specimen had a concentration of Hg in muscle > 1.0 mg kg− 1. Data were limited for specimens > 90 cm long, and further studies on contaminants in larger-bodied skates could usefully be undertaken.