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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 )

Les recommandations de l’Ifremer formulées dans ce document ont pour objectif de permettre une approche et une évaluation homogène du compartiment « qualité de l’eau et des sédiments » pour les contaminants chimiques dans le cadre de l’évaluation de l'état initial, de l’état de référence dans les zones d’implantation des futurs parcs éoliens en mer et de leur suivi sur l’ensemble du territoire.

Within the MONITOOL project, after exploring the relationships between dissolved and labile metal concentrations, a methodology has been proposed for the adaptation of EQS marine water to DGTs, for cadmium, nickel and lead by establing linear model and previous WP6 deliverable. This was accomplished by using a robust database of total dissolved and DGT-labile metal concentrations obtained by concurrent sampling (i.e., spot sampling and DGT) in transitional and coastal waters of the eight European countries participating in the MONITOOL project (EAPA 565/2016). As part of the MONITOOL extension (2021-2023), an additionnal sampling campaign was done (2022) at sites known or suspected to be higly contaminated (in coastal area, estuary and closed bassin) in order to complete the dataset in high concentrations with data close to or even above the EQS marine water values. The objective was to increase the range of validity of the original models to include higher concentrations levels (near/above the EQS marine water). In case the 2022 data doesn’t improve the model, they can be used as “additionnal data” to check the fitness of the original MONITOOL models.

The overarching objective of the MONITOOL project is to improve the implementation of the European Water Framework Directive (WFD, 2000/60/CE) for the assessment of chemical status of transitional and coastal waters, allowing the use of passive sampling devices in a regulatory context. The MONITOOL project provides a robust database of dissolved and labile metal concentrations in transitional and coastal waters, which is used to adapt existing Environmental Quality Standards (EQS; 0.45 µm filtered) to suitable EQSDGT for passive sampling devices. In the framework of the WP6 - action 1, it has been proposed two approaches to use the DGT results for the chemical status assessment: either interpret DGT labile concentration to EQS DGT or predict metals dissolved concentration from their concentration in DGT and compare it to the EQS marine water. DGT EQS are proposed for cadmium, nickel and lead, and a model can be used to predict the concentration in the dissolved fraction from DGT results. Currently, to assess the chemical status of a waterbody regarding Pb, Cd or Ni, the Directive requires to compare the average monthly concentrations measured in spot water samples (analysis on filtered water) for one year (12 results) per WFD cycle (every 6 years) to the EQS marine water (AA - Annual Average - EQS). In this document a simulation of the “chemical status” assessment based on the MONITOOL results is done for each sampling site, using results from spot water samples compared to AA-EQS marine water, ii) using the DGT results compared to the adpated EQS DGT and iii) using the predicted metal dissolved concentration from its DGT results and compare to the EQS marine water. The scope of this deliverable is to update the simulation of the chemical status by using the results of the 2022 campaign (additional campaign - MONITOOL extension).

The Atlas of Chemical Contamination in the Marine Environment is now available on the website Ifremer/CCEM/ Chemical Risk: https://ccem.ifremer.fr/Risque‐Chimique/Atlas‐contamination‐chimique‐en‐milieu‐marin#/map This Atlas can be used to display and overlay different thematic layers of interest related to the monitoring of chemical contaminants, uses, occupations and pressures on the on the land-sea continuum and the sea-sea continuum and facilitates access to monitoring data., L’Atlas Contamination Chimique en milieu marin est désormais accessible sur le site web Ifremer/CCEM/ Risque chimique : https://ccem.ifremer.fr/Risque‐Chimique/Atlas‐contamination‐chimique‐en‐milieu‐marin#/map Cet Atlas permet de visualiser et de superposer différentes couches thématiques d’intérêt en lien avec la surveillance des contaminants chimiques, les usages, occupations et pressions sur le continuum terre‐mer et le continuum mer‐mer et facilite l’accès aux données de surveillance.

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.

Ce rapport fait le bilan de la surveillance de la contamination chimique opérée par l’Ifremer, en partenariat avec l’agence de l’eau Rhône Méditerranée Corse, entre 1998 et 2018. Il présente sur la forme de graphiques et de cartes les principaux résultats obtenus durant cette période ainsi que l’évolution des méthodes et des stratégies de surveillance des eaux côtières de Méditerranée.

As DGT results cannot be directly compared to marine water AA-EQS, the general objective of this document is to propose a methodology so that DGT results can be applied in a regulatory context for waterbody quality assessment. Using a pragmatic approach applied to the context of the WFD, this methodology is based on the study of European reports, European technical and scientific guidance documents, publications of network of experts and processing of MONITOOL dataset. For this purpose, the document is organised in two parts: - a bibliographic part with a review of the derivation process of EQSs, a description of the differences between DGT and spot sampling based measurements, the proposed methodology for the use of DGT results in a regulatory framework, by comparing DGT results to EQS ; - a data processing part carried out using MONITOOL datasets in order to adapt EQS marine water in EQSDGT for Cd, Ni and Pb. Moreover, another methodology is proposed, which is to predict the concentrations measured by DGT into its corresponding dissolved concentrations, so they can be directly compared to EQSmarine water.

As DGT results cannot be directly compared to marine water thresholds, the specific objectives of this document is i) to propose a methodology so that DGT results can be applied in a regulatory context notably for establishing the ecological status of waterbodies as regard specific pollutants and ii) to adapt existing thresholds, defined in marine water at national level by a Member State, into DGT thresholds, for cobalt, copper, iron, zinc and manganese. In order to reach these objectives, an overview of existing thresholds defined for Co, Cu, Fe, Zn and Mn was done, based both on a threshold research in existing databases and on a survey carried on among the MONITOOL partners on the specific pollutant they have defined. The methodology defined for Pb, Cd, and Ni (WP6 ] action 1) is declined for Co, Cu, Fe, Zn and Mn. Based on the robust MONITOOL database of dissolved and labile metal concentrations in transitional and coastal waters, a data processing was done in order to propose adapted DGT thresholds.

In this document a simulation of the gchemical statush assessment based on the MONITOOL results is done for each sampling site, using i) results from spot water samples compared to AA]EQS marine water, ii) using the DGT results compared to the proposed EQS DGT and iii) using the predicted metal concentration in the dissolved fraction from its DGT results and compare to the EQS marine water. The aim of this work is to check the agreement of the assessment using these different approaches, and, in case of mismatching, to check whether the use of DGT results is at least as protective as the current assessment for the Directive.

Dans le cadre du Réseau de Surveillance Prospective, un volet littoral est décliné en 2019, avec l’objectif de proposer un dispositif de recherche des substances d’intérêt émergent (contaminants of emerging concern - CEC) en milieu marin qui permettre in fine d’alimenter la liste des substances pertinentes candidates aux PSEE (Polluants Spécifiques de l’Etat Ecologique). Cela se traduit par l’élaboration en 2019 d’une stratégie d’acquisition de données (substances, matrices, points d’échantillonnage, fréquence et période) et sa déclinaison opérationnelle pour une acquisition de données en 2020-2022. Le principe est d’assurer la pérennité et l’évolutivité de ce dispositif. L’élaboration de cette stratégie s’appuie sur les travaux engagés depuis plus de 10 années par l’Ifremer sur les échantillonneurs passifs en lien avec l’AFB et Aquaref et sur l’expertise et la mise en œuvre de la surveillance environnementale opérées via le ROCCH et le projet de recherche Veille-POP.

The fast-growing offshore wind industry represents a potential new anthropogenic pressure for the marine environment. Despite the fact that it is considered as a green/clean energy source, the large-scale deployment of these devices could induce some environmental impacts that need to be studied. Understanding these impacts is in line with the Marine Strategy Framework Directive (MSFD) (European Commission, 2008) of the European Union which targets good environmental status for the marine environment. The development of offshore renewable energies (ORE), in particular floating and fixed offshore wind structures in France, gives rise to new and more precise questioning from the French public authorities and civil society. In particular, a lot of questions have emerged in relation to the use of Galvanic Anode Cathodic Protection (GACP) systems and about the release of heavy metals associated with their functioning. These anodes are composed of different metals which are more reducing than the metal to be protected. The anodes are generally made with magnesium, aluminium or zinc. In offshore industries such as offshore wind turbines or oil & gas platforms, the anodes used are mainly composed of an aluminium alloy which contains zinc and other trace metals. Their installation in fishing zones is a source of major concern and this affects several offshore wind farm projects (such as Île d’Yeu and Noirmoutier). This growing concern from public authorities and civil society has even led to galvanic anodes being abandoned in certain projects in order to overcome this problem. For example, the chosen solution for the jacket foundations of the Dieppe Le Tréport project is to implement cathodic protection by impressed current (ICCP) with titanium anodes). GACP has been replaced by ICCP in several projects although no scientific study has been conducted to prove the environmental impact of GACP in the ORE context, and no scientific study has proven that ICCP has no environment

L’évaluation de la qualité chimique du milieu marin s’appuie, depuis près de 40 ans en France, sur la recherche des substances dans des espèces sentinelles et intégratrices : les mollusques (moules, huîtres). La bioaccumulation au sein de ces organismes permet de quantifier des contaminants chimiques présents à l’état de trace dans le milieu environnant. De façon à développer une surveillance plus appropriée au milieu marin, un travail de détermination de valeurs guides environnementales (VGE) sur les mollusques, alternatives aux Normes de Qualité Environnementales (NQE) fixées par la DCE dans l’eau, est engagé par Ifremer depuis 2015 en collaboration avec l’ONEMA / AFB. Les NQE eau sont dérivés en VGE mollusques en utilisant des facteurs de conversion : facteur de bioaccumulation (BAF) et de bioconcentration (BCF). La présente étude concerne les substances de l’état chimique de la DCE disposant de seuils NQE ou VGE applicables aux mollusques (Sire, Amouroux, 2016). L’objectif est de vérifier 1) la cohérence des seuils mollusques existants (DCE et OSPAR) et 2) de les confronter aux données de surveillance disponibles. Les résultats acquis par le ROCCH sur la période 2009-2014 sont traités et interprétés vis-à-vis des seuils mollusques (VGE, NQE, EAC, BAC et EC). Ces deux étapes permettent de mettre en évidence 3) les substances pour lesquelles aucune comparaison vis à vis du seuil VGE mollusques n’est possible (pas de seuil OSPAR et pas de résultats ROCCH) et 4) d’identifier les substances pour lesquelles le seuil VGE mollusques paraît ou non applicable.

Dans le cadre de la convention Ifremer - Onema (Action 32), une note est réalisée, elle fait le bilan 2016 de la Contribution a la priorisation des substances et a la prise en compte des données chimiques du milieu marin dans les exercices de priorisation.