Persistent contaminants in adipose fins of returning adult salmonids to the river Tees (UK).

We report on concentrations of polybrominated diphenylethers (PBDEs), polychlorinated biphenyls (PCBs), dichlorodiphenyldichloroethylene (p,p'-DDE) and hexachlorobenzene (HCB) measured in the adipose fins of returning adult Atlantic salmon (Salmo salar) and sea trout (Salmo trutta) to the river Tees in the Northeast of England. Overall, higher concentrations of these contaminants were found in sea trout samples, where detected congeners reflected the more widely used commercial formulations, in particular for the PBDEs. Our results suggest that these fish could be bioaccumulating persistent organic pollutants via diet during their migratory routes (North Sea and the Norwegian Sea) and, in addition, some level of re-mobilisation of these compounds could still be occurring in the UK eastern coastal areas. The use of adipose fin of returning salmonids could be further developed as a non-lethal approach to assess whether persistent contaminants are being accumulated during the juvenile to adult phase of salmonids originating from UK rivers.

PCB pollution continues to impact populations of orcas and other dolphins in European waters.

Organochlorine (OC) pesticides and the more persistent polychlorinated biphenyls (PCBs) have well-established dose-dependent toxicities to birds, fish and mammals in experimental studies, but the actual impact of OC pollutants on European marine top predators remains unknown. Here we show that several cetacean species have very high mean blubber PCB concentrations likely to cause population declines and suppress population recovery. In a large pan-European meta-analysis of stranded (n = 929) or biopsied (n = 152) cetaceans, three out of four species:- striped dolphins (SDs), bottlenose dolphins (BNDs) and killer whales (KWs) had mean PCB levels that markedly exceeded all known marine mammal PCB toxicity thresholds. Some locations (e.g. western Mediterranean Sea, south-west Iberian Peninsula) are global PCB "hotspots" for marine mammals. Blubber PCB concentrations initially declined following a mid-1980s EU ban, but have since stabilised in UK harbour porpoises and SDs in the western Mediterranean Sea. Some small or declining populations of BNDs and KWs in the NE Atlantic were associated with low recruitment, consistent with PCB-induced reproductive toxicity. Despite regulations and mitigation measures to reduce PCB pollution, their biomagnification in marine food webs continues to cause severe impacts among cetacean top predators in European seas.

Reproductive Failure in UK Harbour Porpoises Phocoena phocoena: Legacy of Pollutant Exposure?

Reproductive failure in mammals due to exposure to polychlorinated biphenyls (PCBs) can occur either through endocrine disrupting effects or via immunosuppression and increased disease risk. To investigate further, full necropsies and determination of summed 25 polychlorinated biphenyls congeners (∑PCBs lipid weight) in blubber were undertaken on 329 UK-stranded female harbour porpoises (1990-2012). In sexually mature females, 25/127 (19.7%) showed direct evidence of reproductive failure (foetal death, aborting, dystocia or stillbirth). A further 21/127 (16.5%) had infections of the reproductive tract or tumours of reproductive tract tissues that could contribute to reproductive failure. Resting mature females (non-lactating or non-pregnant) had significantly higher mean ∑PCBs (18.5 mg/kg) than both lactating (7.5 mg/kg) and pregnant females (6 mg/kg), though not significantly different to sexually immature females (14.0 mg/kg). Using multinomial logistic regression models ΣPCBs was found to be a significant predictor of mature female reproductive status, adjusting for the effects of confounding variables. Resting females were more likely to have a higher PCB burden. Health status (proxied by "trauma" or "infectious disease" causes of death) was also a significant predictor, with lactating females (i.e. who successfully reproduced) more likely to be in good health status compared to other individuals. Based on contaminant profiles (>11 mg/kg lipid), at least 29/60 (48%) of resting females had not offloaded their pollutant burden via gestation and primarily lactation. Where data were available, these non-offloading females were previously gravid, which suggests foetal or newborn mortality. Furthermore, a lower pregnancy rate of 50% was estimated for "healthy" females that died of traumatic causes of death, compared to other populations. Whether or not PCBs are part of an underlying mechanism, we used individual PCB burdens to show further evidence of reproductive failure in the North-east Atlantic harbour porpoise population, results that should inform conservation management.

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.

Spatial and temporal analysis of the risks posed by polycyclic aromatic hydrocarbon, polychlorinated biphenyl and metal contaminants in sediments in UK estuaries and coastal waters.

The environmental risks of 22 contaminants, comprising 6 metals, 10 PAHs and 6 PCB congeners occurring in UK estuaries and coastal waters were assessed as single substances. Sediment samples were taken within 12 nautical miles of the English and Welsh coastlines between 1999 and 2011. The measured environmental concentrations were compared to quality standards including ERL, ERM and EAC, all of which have been established internationally. Out of a total of 38,031 individual samples analysed, 42.6% and 7.7% exceeded the ERL/EAC and ERM values, respectively. The highest Risk Characterisation Ratios (RCRs) for metals, PAHs and PCBs were observed for copper, fluorene and CB118 (2,3',4,4',5-pentachlorobiphenyl). In general, the highest concentrations of PAHs and PCBs were observed in 2011 in the Lower Medway indicating a potential risk to the aquatic environment. This study suggests that re-suspension of contaminants banned over 20years ago is still an ongoing issue.

Polycyclic aromatic hydrocarbons in sediments at dredged material disposal sites around England: concentrations in 2013 and time trend information at selected sites 2008-2013.

The maintenance of navigation channels to ports and the development of their facilities present a need to conduct dredging operations, and the subsequent disposal of dredged material at sea. Contaminant concentrations in candidate dredged material are determined and their possible impacts considered during the licensing process, which can result in the exclusion of some material from sea disposal. Monitoring of disposal sites is conducted in order to ensure that no undesirable impacts are occurring. In this study we consider the levels of polycyclic aromatic hydrocarbons (PAHs) in sediments at a number of disposal sites monitored in 2013 and variations in concentrations over time at three sites during the period 2008-2013. These were assessed using established sediment quality guidelines. Elevated PAH concentrations were generally observed only within the boundaries of the disposal sites studied.

Polycyclic aromatic hydrocarbons in fish from St Helena, South Atlantic, in relation to an historic wreck.

Concentrations of polycyclic aromatic hydrocarbons were determined in edible tissues of fish species consumed by the islanders of St Helena to assess any risk to human health posed by oil leaking from an historic wreck. Samples were collected from the vicinity of the wreck site and at two reference locations at which fishing activity occurs. Summed PAH concentrations ranged from 2.2 to 20 µg kg(-1) wet weight, and no PAHs with more than 4 fused rings were detected. All concentrations of the four PAH used as a basis for assessment in relation to health risks to human consumers of foods within the EU (benz[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene and chrysene) were<0.1 µg kg(-1) wet weight and raised no concerns. Additionally, concentrations were calculated as the benzo[a]pyrene toxic equivalency quotient and found to be well below the level of concern (0 to 0.05 µg kg(-1) wet weight benzo[a]pyrene equivalents).

Organohalogen contaminants and trace metals in North-East Atlantic porbeagle shark (Lamna nasus).

The North-East Atlantic porbeagle (Lamna nasus) population has declined dramatically over the last few decades and is currently classified as 'Critically Endangered'. As long-lived, apex predators, they may be vulnerable to bioaccumulation of contaminants. In this study organohalogen compounds and trace elements were analysed in 12 specimens caught as incidental bycatch in commercial gillnet fisheries in the Celtic Sea in 2011. Levels of organohalogen contaminants were low or undetectable (summed CB and BDE concentrations 0.04-0.85 mg kg(-1)wet weight). A notably high Cd concentration (7.2 mg kg(-1)wet weight) was observed in one mature male, whereas the range observed in the other samples was much lower (0.04-0.26 mg kg(-1)wet weight). Hg and Pb concentrations were detected only in single animals, at 0.34 and 0.08 mg kg(-1)wet weight, respectively. These contaminant levels were low in comparison to other published studies for shark species.

An overview of time trends in organic contaminant concentrations in marine mammals: going up or down?

In this article I review recent trends reported in the literature from 2008 to date for organic contaminant concentrations in marine mammal tissues worldwide, in order to get an idea of where we stand currently in relation to the control of hazardous substances. For many contaminants which have been subject to regulation regarding their production and use (e.g. organochlorine pesticides, PBDE and HBCD flame retardants, butyltins) trends are downwards. For perfluorinated compounds, trends are more mixed. For dioxins, furans and dioxin-like CBs, there are no recent data, for either concentrations or trends. For CBs overall, earlier downward trends in concentration in UK harbour porpoises following regulation beginning in the 1980s have stalled, and remain at toxicologically significant levels. This raises concerns for killer whales and bottlenose dolphins who, because of their larger size and greater bioaccumulation potential, have higher levels still, often far above accepted toxicological threshold values.

The principles of effective post-spill environmental monitoring in marine environments and their application to preparedness assessment.

Understanding the fate and effects of marine spills is essential if the scientific and response communities are to develop best practices. The effective deployment of environmental monitoring activity can be complex and requires planning and coordination but the levels of preparedness to deliver the necessary expertise, coordination and funding are often low. This paper identifies and describes the importance of 8 principles of effective post-spill monitoring programmes. These principles are then used in the assessment of monitoring preparedness through the generation of a monitoring preparedness assessment score (MPAS). This approach can be used by local, regional or national authorities to establish the level of preparedness for environmental monitoring and prioritise areas for improvement. It also has value to responders, policy makers, environmental scientists and planners as a tool to assess preparedness and capability for specific scenarios. The approach is demonstrated through the assessment of previous incidents and potential future scenarios.

Levels and trends of PBDEs and HBCDs in the global environment: status at the end of 2012.

In this paper, we have compiled and reviewed the most recent literature, published in print or online from January 2010 to December 2012, relating to the human exposure, environmental distribution, behaviour, fate and concentration time trends of polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants, in order to establish their current trends and priorities for future study. More data are now becoming available for remote areas not previously studied, Indian Ocean islands, for example. Decreasing time trends for penta-mix PBDE congeners were seen for soils in northern Europe, sewage sludge in Sweden and the USA, carp from a US river, trout from three of the Great Lakes and in Arctic and UK marine mammals and many birds, but increasing time trends continue in polar bears and some birds at high trophic levels in northern Europe. This may be partially a result of the time delay inherent in long-range atmospheric transport processes. In general, concentrations of BDE209 (the major component of the deca-mix PBDE product) are continuing to increase. Of major concern is the possible/likely debromination of the large reservoir of BDE209 in soils and sediments worldwide, to yield lower brominated congeners which are both more mobile and more toxic, and we have compiled the most recent evidence for the occurrence of this degradation process. Numerous studies reported here reinforce the importance of this future concern. Time trends for HBCDs are mixed, with both increases and decreases evident in different matrices and locations and, notably, with increasing occurrence in birds of prey. Temporal trends for both PBDEs and HBCD in Asia are unclear currently. A knowledge gap has been noted in relation to metabolism and/or debromination of BDE209 and HBCD in birds. Further monitoring of human exposure and environmental contamination in areas of e-waste recycling, particularly in Asia and Africa, is warranted. More data on temporal trends of BDE and HBCD concentrations in a variety of matrices and locations are needed before the current status of these compounds can be fully assessed, and the impact of regulation and changing usage patterns among different flame retardants determined.

A temporal and spatial assessment of TBT concentrations at dredged material disposal sites around the coast of England and Wales.

Despite legislative interventions since the 1980s, contemporary concentrations of organotin compounds in marine sediments still impose restrictions on the disposal of dredged material in the UK. Here, we analyse temporal and spatial data to assess the effectiveness of the ban on the use of TBT paints in reducing concentrations at disposal sites. At a national scale, there was a statistically significant increase in the proportion of samples in which the concentration was below the limit of detection (LOD) from 1998 to 2010. This was observed for sediments both inside and outside the disposal sites. However, this temporal decline in organotin concentration is disposal site-specific. Of the four sites studied in detail, two displayed significant increases in proportion of samples below LOD over time. We argue that site-specificity in the effectiveness of the TBT ban results from variations in historical practices at source and unique environmental characteristics of each site.

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.

Evaluating legacy contaminants and emerging chemicals in marine environments using adverse outcome pathways and biological effects-directed analysis.

Natural and synthetic chemicals are essential to our daily lives, food supplies, health care, industries and safe sanitation. At the same time protecting marine ecosystems and seafood resources from the adverse effects of chemical contaminants remains an important issue. Since the 1970s, monitoring of persistent, bioaccumulative and toxic (PBT) chemicals using analytical chemistry has provided important spatial and temporal trend data in three important contexts; relating to human health protection from seafood contamination, addressing threats to marine top predators and finally providing essential evidence to better protect the biodiversity of commercial and non-commercial marine species. A number of regional conventions have led to controls on certain PBT chemicals over several years (termed 'legacy contaminants'; e.g. cadmium, lindane, polycyclic aromatic hydrocarbons [PAHs] and polychlorinated biphenyls [PCBs]). Analytical chemistry plays a key role in evaluating to what extent such regulatory steps have been effective in leading to reduced emissions of these legacy contaminants into marine environments. In parallel, the application of biomarkers (e.g. DNA adducts, CYP1A-EROD, vitellogenin) and bioassays integrated with analytical chemistry has strengthened the evidence base to support an ecosystem approach to manage marine pollution problems. In recent years, however,the increased sensitivity of analytical chemistry, toxicity alerts and wider environmental awareness has led to a focus on emerging chemical contaminants (defined as chemicals that have been detected in the environment, but which are currently not included in regulatory monitoring programmes and whose fate and biological impacts are poorly understood). It is also known that natural chemicals (e.g. algal biotoxins) may also pose a threat to marine species and seafood quality. Hence complex mixtures of legacy contaminants, emerging chemicals and natural biotoxins in marine ecosystems represent important scientific, economic and health challenges. In order to meet these challenges and pursue cost-effective scientific approaches that can provide evidence necessary to support policy needs (e.g. the European Marine Strategy Framework Directive), it is widely recognised that there is a need to (i) provide marine exposure assessments for priority contaminants using a range of validated models, passive samplers and biomarkers; (ii) integrate chemical monitoring data with biological effects data across spatial and temporal scales (including quality controls); and (iii) strengthen the evidence base to understand the relationship between exposure to complex chemical mixtures, biological and ecological impacts through integrated approaches and molecular data (e.g. genomics, proteomics and metabolomics). Additionally, we support the widely held view that (iv) that rather than increasing the analytical chemistry monitoring of large number of emerging contaminants, it will be important to target analytical chemistry towards key groups of chemicals of concern using effects-directed analysis. It is also important to evaluate to what extent existing biomarkers and bioassays can address various classes of emerging chemicals using the adverse outcome pathway (AOP) approach now being developed by the Organization for Economic Cooperation and Development (OECD) with respect to human toxicology and ecotoxicology.

What caused the UK's largest common dolphin (Delphinus delphis) mass stranding event?

On 9 June 2008, the UK's largest mass stranding event (MSE) of short-beaked common dolphins (Delphinus delphis) occurred in Falmouth Bay, Cornwall. At least 26 dolphins died, and a similar number was refloated/herded back to sea. On necropsy, all dolphins were in good nutritive status with empty stomachs and no evidence of known infectious disease or acute physical injury. Auditory tissues were grossly normal (26/26) but had microscopic haemorrhages (5/5) and mild otitis media (1/5) in the freshest cases. Five lactating adult dolphins, one immature male, and one immature female tested were free of harmful algal toxins and had low chemical pollutant levels. Pathological evidence of mud/seawater inhalation (11/26), local tide cycle, and the relative lack of renal myoglobinuria (26/26) suggested MSE onset on a rising tide between 06:30 and 08∶21 hrs (9 June). Potential causes excluded or considered highly unlikely included infectious disease, gas/fat embolism, boat strike, by-catch, predator attack, foraging unusually close to shore, chemical or algal toxin exposure, abnormal weather/climatic conditions, and high-intensity acoustic inputs from seismic airgun arrays or natural sources (e.g., earthquakes). International naval exercises did occur in close proximity to the MSE with the most intense part of the exercises (including mid-frequency sonars) occurring four days before the MSE and resuming with helicopter exercises on the morning of the MSE. The MSE may therefore have been a "two-stage process" where a group of normally pelagic dolphins entered Falmouth Bay and, after 3-4 days in/around the Bay, a second acoustic/disturbance event occurred causing them to strand en masse. This spatial and temporal association with the MSE, previous associations between naval activities and cetacean MSEs, and an absence of other identifiable factors known to cause cetacean MSEs, indicates naval activity to be the most probable cause of the Falmouth Bay MSE.

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.

A novel abbreviation standard for organobromine, organochlorine and organophosphorus flame retardants and some characteristics of the chemicals.

Ever since the interest in organic environmental contaminants first emerged 50years ago, there has been a need to present discussion of such chemicals and their transformation products using simple abbreviations so as to avoid the repetitive use of long chemical names. As the number of chemicals of concern has increased, the number of abbreviations has also increased dramatically, sometimes resulting in the use of different abbreviations for the same chemical. In this article, we propose abbreviations for flame retardants (FRs) substituted with bromine or chlorine atoms or including a functional group containing phosphorus, i.e. BFRs, CFRs and PFRs, respectively. Due to the large number of halogenated and organophosphorus FRs, it has become increasingly important to develop a strategy for abbreviating the chemical names of FRs. In this paper, a two step procedure is proposed for deriving practical abbreviations (PRABs) for the chemicals discussed. In the first step, structural abbreviations (STABs) are developed using specific STAB criteria based on the FR structure. However, since several of the derived STABs are complicated and long, we propose instead the use of PRABs. These are, commonly, an extract of the most essential part of the STAB, while also considering abbreviations previously used in the literature. We indicate how these can be used to develop an abbreviation that can be generally accepted by scientists and other professionals involved in FR related work. Tables with PRABs and STABs for BFRs, CFRs and PFRs are presented, including CAS (Chemical Abstract Service) numbers, notes of abbreviations that have been used previously, CA (Chemical Abstract) name, common names and trade names, as well as some fundamental physico-chemical constants.

Butyltin compounds in liver of harbour porpoises (Phocoena phocoena) from the UK prior to and following the ban on the use of tributyltin in antifouling paints (1992-2005 & 2009).

Liver butyltin concentrations (monobutyl, dibutyl and tributyltin (TBT)) in harbour porpoises (n=410) have been determined during 1992-2005, and again in 2009 following a ban on the use of tributyltin-based antifouling paints on ships. The aim was to assess the effectiveness of the regulation, which was implemented during 2003-2008. Since the ban was put in place summed butyltin concentrations have declined. Also, the percentage of animals in which TBT was detected has fallen sharply, indicating the cessation of fresh inputs. In 1992, 1993 and 1995, TBT was detected in 100% of samples analysed. In 2003-2005, once the implementation of the ban had begun, this fell to 61-72%, and in 2009, following the completion of the ban, had reduced to 4.3% (i.e. in only 1 of 23 samples analysed). Thus we conclude that the ban has proved effective in reducing TBT inputs to the seas from vessels.