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.

Trends of legacy and emerging organic contaminants in a sediment core from Cienfuegos Bay, Cuba, from 1990 to 2015.

Legacy and emerging organic pollutants pose an ever-expanding challenge for the marine environment. This study analysed a dated sediment core from Cienfuegos Bay, Cuba, to assess the occurrence of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), alternative halogenated flame retardants (aHFRs), organophosphate esters (OPEs), and phthalates (PAEs) from 1990 to 2015. The results evidence the continuing presence of historical regulated contaminants (PCBs, OCPs, and PBDEs) in the southern basin of Cienfuegos Bay. PCB contamination declined since 2007, likely in response to the gradual global phasing out of PCB containing materials. There have been relatively consistent low accumulation rates for OCPs and PBDEs at this location (in 2015 approximately 1.9 and 0.26ng/cm2/year, respectively, with 2.8ng/cm2/year for Σ6PCBs), with indications of recent local DDT use in response to public health emergencies. In contrast, sharp increases are observed between 2012 and 2015 for the contaminants of emerging concern (PAEs, OPEs, and aHFRs), and in the case of two PAEs (DEHP and DnBP) the concentrations were above the established environmental effect limits for sediment dwelling organisms. These increasing trends reflect the growing global usage of both alternative flame retardants and plasticizer additives. Local drivers for these trends include nearby industrial sources such as a plastic recycling plant, multiple urban waste outfalls, and a cement factory. The limited capacity for solid waste management may also contribute to the high concentrations of emerging contaminants, especially plastic additives. For the most recent year (2015), the accumulation rates for Σ17aHFRs, Σ19PAEs, and Σ17OPEs into sediment at this location were estimated to be 10, 46 000, and 750ng/cm2/year, respectively. This data provides an initial survey of emerging organic contaminants within this understudied region of the world. The increasing temporal trends observed for aHFRs, OPEs, and PAEs highlights the need for further research concerning the rapid influx of these emerging contaminants.

Extruded polystyrene microplastics as a source of brominated flame retardant additives in the marine environment: long-term field and laboratory experiments.

Microplastics (MPs) in the environment have become a global concern, not only for the physical effects of the plastic particles themselves but also for being vectors of chemical additives. In this context, little is known about the ability of MPs, particularly extruded polystyrene microplastics (XPS-MPs), to release organic chemical additives in the marine environment. In this study, a series of field and laboratory experiments were carried out to determine the leaching behaviour of organic additives including brominated flame retardants from XPS-MPs into seawater. The conducted experiments confirmed a rapid release of bisphenol A (BPA), 2,4,6-tribromophenol (TBP), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (α-, ß-, and γ-HBCDD) from the studied MPs followed by a slower rate of release over time. The effects of environmental factors on the leaching rates of these additives were also examined. Increasing Dissolved Organic Matter (DOM) concentrations and the temperature of the seawater enhanced the release of additives by increasing their solubility and polymer flexibility. In contrast, pH tested at 7, 7.5 and 8 was found to have a minor effect on additives leaching; and salinity negatively affected the leaching rate likely due to their reduced solubility and reduced diffusion from the MPs. The present study provides empirical evidence of the behaviour of XPS-MPs as a source of organic additives in the marine environment that merit further investigation.

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.

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.

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.

Decabromodiphenylether trends in the European environment: Bird eggs, sewage sludge and surficial sediments.

Concern on relatively high levels and the potential bioaccumulation of decabromodiphenylether (BDE209) has led to a European 8-year monitoring program on trends in BDE209 concentrations in birds, sewage sludge and sediments from seven countries. BDE209 was analysed in four environmental matrices: sparrowhawk eggs (UK), glaucous gull eggs (Bear Island, Norway), sewage sludge (UK, Ireland and the Netherlands) and sediment (France, Germany, the Netherlands, UK and Ireland). BDE209 was detected in most of the glaucous gull and sparrow hawk eggs but neither increasing nor decreasing trends in these BDE209 levels were observed. An indication for debromination of BDE209 in sparrowhawk eggs was found. BDE209 concentrations in sediments ranged from very low ng/g (88 ng/g on an organic carbon (OC) basis) concentrations, in the rivers Elbe, Ems, Seine and the Outer Humber, to high µg/g (120 µg/g OC), in the Western Scheldt, Liverpool Bay and River Mersey. Apart from decreasing values in the Western Scheldt sediment no further decreases in BDE209 concentrations were observed over time, neither in sediment nor in sewage sludge showing that the voluntary emissions control program of the bromine industry only had a local effect. In contrast to the sewage sludge samples from the Netherlands (mean 355 ng/g dry weight (dw) or 1026 ng/g OC), the BDE209 concentrations in the UK increased at all sites from 2006 to 2011 (8092 ng/g dw or 22,367 ng/g OC). The BDE209 levels in several UK sediments and sewage sludge were still very high at the end of the program in 2012, most likely caused by frequent use of BDE209 in the textile industry. This may be indicative of the persistence of BDE209 and the limited degradation into lower brominated congeners in sediment, although it cannot be excluded that ongoing BDE209 emissions have played a role as well.

Detecting illegal cyanide fishing: Establishing the evidence base for a reliable, post-collection test.

Ornamental fish have been legally harvested since the 1930's but in the 60's, cyanide fishing was first documented. Target fish exposed to the chemical are temporarily paralysed making them easier to catch, but with high post-capture mortality and significant ecological impacts, its use is banned in most exporting countries. To differentiate illegally caught fish from those sustainably collected, efforts to develop a post-collection detection test began nearly 30 years ago. However, even the most promising approach has been questioned by other researchers as unrepeatable under different experimental conditions. In this paper we summarise the evidence-base for establishing a cyanide detection test for live fish by evaluating current approaches. We describe the key knowledge gaps which continue to limit our progress in implementing a screening programme and highlight some alternative solutions which may provide greater short to medium term opportunities to prevent the illegal practise before fish enter the supply chain.

Organophosphorus flame retardants (PFRs) and plasticisers in harbour porpoises (Phocoena phocoena) stranded or bycaught in the UK during 2012.

A suite of twenty organophosphorus flame retardant compounds have been determined in blubber and liver tissue of twenty harbour porpoises stranded or bycaught in the UK during 2012 in order to establish current levels of contamination. Fourteen of the twenty compounds were below the limits of quantification in all samples. Six could be quantified at maximum concentrations (in blubber) between 6.7 and 246µgkg(-1) wet weight. These levels do not suggest a high level of concern regarding potential impacts and do not indicate that routine monitoring in UK porpoises is warranted at this time.

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 35µgkg(-1) wet weight. This contrasted with those of the BDEs, summed concentrations which ranged from 54.6 to 913µgkg(-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 1.7µgkg(-1) wet weight) and the four nona- and deca-BDE congeners were not detected in any sample.

Organochlorine pesticides and chlorobiphenyls in the blubber of bycaught female common dolphins from England and Wales from 1992-2006.

We report concentrations of organochlorine pesticides (HCB, HCHs, DDTs, dieldrin) and PCBs in the blubber of 43 common dolphins bycaught in fisheries operating off the SW coast of the UK from 1992 to 2006. Concentrations of ΣDDT (summed p,p'-DDT and its metabolites, p,p'-DDE and p,p'-TDE) and of 25 summed CB congeners ranged from 0.2 to 16.1 and 2.1 to 62.4 mg kg(-1) lipid weight, respectively. Concentrations of sum HCH, HCB and dieldrin were lower, ranging from not detected to 0.14, 0.01 to 0.27 and 0.01 to 0.73 mg kg(-1) lipid weight, respectively. All contaminants studied showed a downward time trend but only that for HCHs was statistically significant. Overall, 72% of the dolphins analysed had blubber PCB concentrations above an established toxicity threshold value.

Contaminants in cetaceans from UK waters: status as assessed within the Cetacean Strandings Investigation Programme from 1990 to 2008.

Since 1990, tissue samples from UK-stranded and -bycaught cetaceans have been available for study of contaminant burdens. These have been used to study spatial and temporal trends in concentrations in UK waters, and to investigate potential associations between contaminants and health status. We describe the current status of cetaceans (primarily harbour porpoises, Phocoena phocoena) in UK waters in relation to pollution. Concentrations of BDEs, HBCD, and the organochlorine pesticides are declining. In contrast, concentrations of CBs have plateaued following earlier reductions due to regulation of use, and further reductions are likely to take decades. Blubber PCB concentrations are still at toxicologically significant levels in many harbour porpoises and regularly occur at even higher levels in bottlenose dolphins and killer whales due to their higher trophic level in marine food chains. Further reductions in PCB inputs into the marine environment are needed to mitigate risk from PCB exposure in these species.

A review of the analysis of novel brominated flame retardants.

This review provides a summary of various analytical methodologies applied to the determination of "novel" brominated flame retardants (NBFRs) in various environmental compartments, as reported in peer reviewed literature, either in print or online, until the end of 2010. NBFRs are defined here as those brominated flame retardants (BFRs) which are either new to the market or newly/recently observed in the environment. The preparation and extraction of sediment, water, sewage sludge, soil, air and marine biota samples, the extract clean-up/fractionation and subsequent instrumental analysis of NBFRs are described and critically examined. Generally, while the instrumental analysis step mainly relies on mass-spectrometric detection specifically developed for NBFRs, and hyphenated to liquid or gas chromatography, preceding steps tend to replicate methodologies applied to the determination of traditional BFRs such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). Shortcomings and gaps are discussed and recommendations for future development are given.

Decabromodiphenylether and hexabromocyclododecane in wild birds from the United Kingdom, Sweden and The Netherlands: Screening and time trends.

The brominated flame retardant decabromodiphenylether (DBDE) was analysed in wild birds to identify the most suitable species for monitoring time trends in DBDE contamination. This information was later used for the design of a 10-year trend study on DBDE in the European Union. DBDE was measured in muscle tissue, liver, and eggs from 10 terrestrial and four aquatic bird species. DBDE was detected in 47% of the terrestrial bird samples (nine species) and in 9% of the aquatic bird samples (six species). Peregrine falcon and sparrowhawk specimens were selected as most suitable species to determine temporal trends of DBDE. For sparrowhawks, no significant change in DBDE concentrations between 1973 and 2001 was found, although in later years more DBDE concentrations were above the detection limit. Peak DBDE levels measured in peregrines in 1995, were followed by a decline in concentrations until 2001. The same species were used for a trend study on hexabromocylcododecane (HBCD). Twenty-four percent of peregrine falcon eggs and 12% of sparrowhawk muscle samples demonstrated measurable HBCD residues. Three diastereomers of HBCD were analysed and the α-diastereomer was the predominant one in most samples. No clear time trends were observed for HBCD in either species. This study demonstrated that these DBDE and HBCD are bioavailable to birds of Northern Europe, although bioaccumulation seems to occur to a limited extent.

Levels and trends of brominated diphenyl ethers in blubber of harbor porpoises (Phocoena phocoena) from the U.K., 1992-2008.

Controls were placed on the production and use of the penta-mix polybrominated diphenyl ether (PBDE) formulation within the European Union in 2004. In porpoises stranded or bycaught around the U.K., BDE congeners from this product predominate. Lipid-normalized concentrations of 9 (summed) BDE congeners in the blubber of 415 porpoises sampled during the period 1992-2008 have been investigated for possible time trends resulting from the regulatory action. Our analysis suggests that, overall, median Sigma9BDE concentrations peaked around 1998 and have since reduced by between 53.8% and 73.5% to 2008. Our best point estimate is that the reduction has been 67.6%. This decline was highly statistically significant (p < 0.001) and was not confounded by a range of other factors which were also considered (area, season, nutritional status, bycaught/stranded, and age class).

Chlorobiphenyls in the blubber of harbour porpoises (Phocoena phocoena) from the UK: levels and trends 1991-2005.

Harbour porpoises sampled within the UK Cetacean Strandings Investigation Programme have been analysed for 25 chlorobiphenyl congeners. In all, 440 porpoises stranded or bycaught during the period 1991-2005 were studied. There are regional differences in the trend in summed congener concentrations over time but, despite controls on PCBs having been in place for decades, they are declining only slowly. Their toxic impacts in UK porpoises - increased susceptibility to infectious disease mortality in the most contaminated individuals - looks likely to continue for some time yet. Further efforts to limit or eliminate PCB discharges to the marine environment are still needed.

The model anti-androgen flutamide suppresses the expression of typical male stickleback reproductive behaviour.

Over the past 15 years considerable attention has been given to the presence in the environment of endocrine disrupting chemicals (EDCs) that may have harmful effects on organisms. Specific test guidelines for the detection of EDCs used for short-term fish screening assays have been developed by the Organisation for Economic Cooperation and Development (OECD). Compared to the core species used in the OECD guidelines, the three-spined stickleback (Gasterosteus aculeatus) has an additional and unique endpoint for (anti-)androgenic substances through the androgen-dependent glue protein (spiggin) used in the nest building. Here we describe a specific behavioural assay that was developed in parallel to the OECD protocol, utilising unique behavioural features of sticklebacks. In the assay, a photoperiod of 16L:8D (light:dark) and a temperature of 17+/-1 degrees C was used to induce breeding in quiescent male sticklebacks that were simultaneously exposed for a 21-day period to the mammalian anti-androgen flutamide (FL) at 100, 500 and 1000 microg/l (plus a water control). Spiggin production and the reproductive behaviour (nest building and courtship) of male sticklebacks were the main measured endpoints. The control fish entered an active breeding cycle including nest building and courtship behaviours as expected due to the stimulating temperature and photoperiodic conditions. The FL-exposed males showed significantly lower spiggin levels at 500 and 1000 microg/l. In addition, there was a significant decrease in the number of nests built by the FL-treated males at 100 microg/l with no nest built at 500 and 1000 microg/l. Finally, FL affected the courtship behaviour of the males with a significant reduction of the number of zigzags towards the female. When the breeding status of the stickleback males is controlled, the behavioural assay developed here is a suitable tool for the detection of androgen antagonists.

Levels and trends of HBCD and BDEs in the European and Asian environments, with some information for other BFRs.

In this paper, we review recent data for brominated flame retardants (particularly BDEs, HBCD and TBBP-A) in samples from the European and Asian environments, including recent temporal trend studies. Research is active and we cite over 100 studies published during 2005-2007. Environmental compartments studied comprise the atmosphere, indoor and outdoor air, sewage sludges, soils and sediments and a variety of biological samples and food chains. Findings include that the lack of reference materials for use in analytical quality control and method validation identified earlier has been addressed, and certified concentrations are now available for a number of BDE congeners in six pre-existing and one new reference materials. BDE209 was certified in three samples of indoor dust. The analysis of BDE209 remains problematic, but suitable methods for its determination are available and need to be applied. The contamination of indoor environments with BFRs has been recognised as representing a significant uptake pathway, particularly via dust. Additional data for TBBP-A are needed from areas, where it is produced and used, primarily Asia, as the worst-case scenario. As a reactive flame retardant it is less likely to leach from finished products. Also, issues regarding the importance of e-waste recycling as a source of BFRs to the local populations and the local environment require urgent study, certainly in China and possibly elsewhere. Generally, trends show a levelling in concentrations of BDEs and increases in concentrations of HBCD wherever determined and BDE209 in Asia.