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

Alternative flame retardants, Dechlorane Plus and BDEs in the blubber of harbour porpoises (Phocoena phocoena) stranded or bycaught in the UK during 2008

Thirty alternative flame retardant compounds and a suite of 17 brominated diphenyl ether (BDE) congeners were determined in the blubber of 21 harbour porpoises stranded or bycaught around UK coasts during 2008 using GC-MS/MS. Of the 30 compounds, 19 were not detected. Of the remaining 11 compounds, some fell below the lowest calibration level and so were recorded as less than values, but were certainly present in the blubber samples (examples include tetrabromo-p-xylene (TBX), tetrabromo-o-chlorotoluene (TBCT) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (TBP-DBPE). Concentrations were low, the highest concentration being only 35 μg kg− 1 wet weight. This contrasted with those of the BDEs, summed concentrations which ranged from 54.6 to 913 μg kg− 1 wet weight, although levels in porpoise blubber have been declining since 1998. Both Dechlorane Plus (DDC-CO) isomers were detected in some samples, suggesting either that this product has been used in the UK or that its presence may result from atmospheric transport from source regions. BDE183, a marker for the octa-mix PBDE product, was found at low concentrations (0.63 to 1.7 μg kg− 1 wet weight) and the four nona- and deca-BDE congeners were not detected in any sample

Alternative flame retardants, Dechlorane Plus and BDEs in the blubber of harbour porpoises (Phocoena phocoena) stranded or bycaught in the UK during 2008

Thirty alternative flame retardant compounds and a suite of 17 brominated diphenyl ether (BDE) congeners were determined in the blubber of 21 harbour porpoises stranded or bycaught around UK coasts during 2008 using GC-MS/MS. Of the 30 compounds, 19 were not detected. Of the remaining 11 compounds, some fell below the lowest calibration level and so were recorded as less than values, but were certainly present in the blubber samples (examples include tetrabromo-p-xylene (TBX), tetrabromo-o-chlorotoluene (TBCT) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (TBP-DBPE). Concentrations were low, the highest concentration being only 35 μg kg− 1 wet weight. This contrasted with those of the BDEs, summed concentrations which ranged from 54.6 to 913 μg kg− 1 wet weight, although levels in porpoise blubber have been declining since 1998. Both Dechlorane Plus (DDC-CO) isomers were detected in some samples, suggesting either that this product has been used in the UK or that its presence may result from atmospheric transport from source regions. BDE183, a marker for the octa-mix PBDE product, was found at low concentrations (0.63 to 1.7 μg kg− 1 wet weight) and the four nona- and deca-BDE congeners were not detected in any sample

Determination of the brominated flame retardant, hexabromocyclododecane, in sediments and biota by liquid chromatography-electrospray ionisation mass spectrometry

A method involving reversed-phase, liquid chromatography coupled to electrospray ionisation mass spectrometry (LC-ESI-MS) was developed for separation, detection and quantitation of the alpha-, beta- and gamma-diastereoisomers of hexabromocyclododecane (HBCD). To address the lack of environmental data of this high-production-volume chemical, and to begin to understand the behaviour, the fate and the effects of these stereoisomers, a diastereoisomer-specific method is necessary. Currently, HBCD stereomeric separation is not possible using gas chromatography; thermally-induced rearrangements as well as decomposition of the compound occur at temperatures > 240 degrees C by the initial elimination of hydrogen bromide. The extraction of HBCDs, and subsequent clean-up procedures are similar to those used for polybrominated diphenylethers, and include Soxhlet, homogenisation, mechanical shaking, sulphuric acid treatment and gel-permeation chromatography. Single-quadrupole and ion-trap mass analysers as well as LC separations were optimised using pure and individual HBCD stereoisomers, and determinations were performed using selected ion monitoring (m/z 640.7) of the [M-H](-) ion. This article presents options for analyte extraction and information regarding instrument optimisation, and demonstrates that LC-MS is a suitable technique for quantifying HBCD stereoisomers in complex environmental matrices