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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.

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.

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 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.