Persistence of PFOA Pollution at a PTFE Production Site and Occurrence of Replacement PFASs in English Freshwaters Revealed by Sentinel Species, the Eurasian Otter (Lutra lutra).

Concentrations of 33 PFASs were determined in 20 Eurasian otters, sampled 2015-2019, along a transect away from a factory, which used PFOA in PTFE manufacture. Despite cessation of usage in 2012, PFOA concentrations remained high near the factory (>298 µg/kg ww <20 km from factory) and declined with increasing distance (<57 µg/kg ww >150 km away). Long-chain legacy PFASs dominated the Σ33PFAS profile, particularly PFOS, PFOA, PFDA, and PFNA. Replacement compounds, PFECHS, F-53B, PFBSA, PFBS, PFHpA, and 8:2 FTS, were detected in ≥19 otters, this being the first report of PFBSA and PFECHS in the species. Concentrations of replacement PFASs were generally lower than legacy compounds (max: 70.3 µg/kg ww and 4,640 µg/kg ww, respectively). Our study underscores the utility of otters as sentinels for evaluating mitigation success and highlights the value of continued monitoring to provide insights into the longevity of spatial associations with historic sources. Lower concentrations of replacement, than legacy, PFASs likely reflect their lower bioaccumulation potential, and more recent introduction. Continued PFAS use will inevitably lead to increased environmental and human exposure if not controlled. Further research is needed on fate, toxicity, and bioaccumulation of replacement compounds.

Spatiotemporal Trends Spanning Three Decades Show Toxic Levels of Chemical Contaminants in Marine Mammals.

Despite their ban and restriction under the 2001 Stockholm Convention, persistent organic pollutants (POPs) are still widespread and pervasive in the environment. Releases of these toxic and bioaccumulative chemicals are ongoing, and their contribution to population declines of marine mammals is of global concern. To safeguard their survival, it is of paramount importance to understand the effectiveness of mitigation measures. Using one of the world's largest marine mammals strandings data sets, we combine published and unpublished data to examine pollutant concentrations in 11 species that stranded along the coast of Great Britain to quantify spatiotemporal trends over three decades and identify species and regions where pollutants pose the greatest threat. We find that although levels of pollutants have decreased overall, there is significant spatial and taxonomic heterogeneity such that pollutants remain a threat to biodiversity in several species and regions. Of individuals sampled within the most recent five years (2014-2018), 48% of individuals exhibited a concentration known to exceed toxic thresholds. Notably, pollutant concentrations are highest in long-lived, apex odontocetes (e.g., killer whales (Orcinus orca), bottlenose dolphins (Tursiops truncatus), and white-beaked dolphins (Lagenorhynchus albirostris)) and were significantly higher in animals that stranded on more industrialized coastlines. At the present concentrations, POPs are likely to be significantly impacting marine mammal health. We conclude that more effective international elimination and mitigation strategies are urgently needed to address this critical issue for the global ocean health.

Anthropogenic Drivers of Variation in Concentrations of Perfluoroalkyl Substances in Otters (Lutra lutra) from England and Wales.

Per- and polyfluoroalkyl substances (PFASs) are ubiquitous environmental contaminants that have been linked to adverse health effects in wildlife and humans. Here, we report the presence of PFASs in Eurasian otters (Lutra lutra) in England and Wales and their association with anthropogenic sources. The following 15 compounds were analyzed: 10 perfluoroalkyl carboxylic acids (PFCAs), 4 perfluoroalkyl sulfonic acids (PFSAs), and perfluorooctane sulfonamide, in livers of 50 otters which died between 2007 and 2009. PFASs were detected in all otters analyzed, with 12/15 compounds detected in ≥80% of otters. Perfluorooctane sulfonate (PFOS) accounted for 75% of the ΣPFAS profile, with a maximum concentration of 6800 µg/kg wet weight (ww). Long-chain (≥C8) PFCAs accounted for 99.9% of the ΣPFCA profile, with perfluorodecanoic acid and perfluorononanoic acid having the highest maxima (369 µg/kg ww and 170 µg/kg ww, respectively). Perfluorooctanoic acid (PFOA) concentrations were negatively associated with the distance from a factory that used PFOA in polytetrafluoroethylene manufacture. Most PFAS concentrations in otters were positively associated with load entering wastewater treatment works (WWTW) and with arable land, suggesting that WWTW effluent and sewage sludge-amended soils are significant pathways of PFASs into freshwaters. Our results reveal the widespread pollution of British freshwaters with PFASs and demonstrate the utility of otters as effective sentinels for spatial variation in PFAS concentrations.

Levels of Polychlorinated Biphenyls Are Still Associated with Toxic Effects in Harbor Porpoises (Phocoena phocoena) Despite Having Fallen below Proposed Toxicity Thresholds.

Polychlorinated biphenyls (PCBs) are toxic, persistent, and lipophilic chemical compounds that accumulate to high levels in harbor porpoises (Phocoena phocoena) and other cetaceans. It is important to monitor PCBs in wildlife, particularly in highly exposed populations to understand if concentrations are declining and how levels relate to toxicological thresholds and indices of health like infectious disease mortality. Here we show, using generalized additive models and tissue samples of 814 U.K.-stranded harbor porpoises collected between 1990 and 2017, that mean blubber PCB concentrations have fallen below the proposed thresholds for toxic effects. However, we found they are still associated with increased rates of infectious disease mortality such that an increase in PCB blubber concentrations of 1 mg kg-1 lipid corresponds with a 5% increase in risk of infectious disease mortality. Moreover, rates of decline and levels varied geographically, and the overall rate of decline is slow in comparison to other pollutants. We believe this is evidence of long-term preservation in the population and continued environmental contamination from diffuse sources. Our findings have serious implications for the management of PCB contamination in the U.K. and reinforce the need to prevent PCBs entering the marine environment to ensure that levels continue to decline.

Fingerprint analysis of brominated flame retardants and Dechloranes in North Sea sediments.

53 brominated and chlorinated flame retardants were investigated in sediment samples from the German rivers Elbe and Weser, the German Bight, Jadebusen, East Frisian Coast as well as the UK East coast. The aim of the presented study was to investigate the prevalence of different halogenated flame retardant groups as contaminants in North Sea sediments, identify determining factors for the distribution and levels as well as to identify area specific fingerprints that could help identify sources. In order to do that a fast and effective ASE extraction method with an on-line clean-up was developed as well as a GC-EI-MSMS and LC-ESI-MSMS method to analyse PBDEs, MeOBDEs, alternate BFRs, Dechloranes as well as TBBPA and HBCDD. A fingerprinting method was adopted to identify representative area-specific patterns based on detection frequency as well as concentrations of individual compounds. Concentrations in general were low, with<1 ng g(-1) dw for most compounds. Exceptions were the comparably high concentrations of BDE-209 with up to 7 ng g(-1) dw in selected samples and TBBPA in UK samples with 2.7±1.5 ng g(-1) dw. Apart from BDE-209 and TBBPA, alternate BFRs and Dechloranes were predominant in all analysed samples, displaying the increasing relevance of these compounds as environmental contaminants.

Potential exposure of pollinators to neonicotinoid insecticides from the use of insecticide seed treatments in the mid-southern United States.

Research was done during 2012 to evaluate the potential exposure of pollinators to neonicotinoid insecticides used as seed treatments on corn, cotton, and soybean. Samples were collected from small plot evaluations of seed treatments and from commercial fields in agricultural production areas in Arkansas, Mississippi, and Tennessee. In total, 560 samples were analyzed for concentrations of clothianidin, imidacloprid, thiamethoxam, and their metabolites. These included pollen from corn and cotton, nectar from cotton, flowers from soybean, honey bees, Apis mellifera L., and pollen carried by foragers returning to hives, preplanting and in-season soil samples, and wild flowers adjacent to recently planted fields. Neonicotinoid insecticides were detected at a level of 1 ng/g or above in 23% of wild flower samples around recently planted fields, with an average detection level of about 10 ng/g. We detected neonicotinoid insecticides in the soil of production fields prior to planting at an average concentration of about 10 ng/g, and over 80% of the samples having some insecticide present. Only 5% of foraging honey bees tested positive for the presence of neonicotinoid insecticides, and there was only one trace detection (< 1 ng/g) in pollen being carried by those bees. Soybean flowers, cotton pollen, and cotton nectar contained little or no neonicotinoids resulting from insecticide seed treatments. Average levels of neonicotinoid insecticides in corn pollen ranged from less than 1 to 6 ng/g. The highest neonicotinoid concentrations were found in soil collected during early flowering from insecticide seed treatment trials. However, these levels were generally not well correlated with neonicotinoid concentrations in flowers, pollen, or nectar. Concentrations in flowering structures were well below defined levels of concern thought to cause acute mortality in honey bees. The potential implications of our findings are discussed.

Evaluation of a marine mammal status and trends contaminants indicator for European waters.

Marine mammals are vulnerable to the bioaccumulation, biomagnification and lactational transfer of specific types of pollutants, such as industrial polychlorinated biphenyls (PCBs), due to their long-life spans, feeding at a high trophic level and unique fat stores that can serve as depots for these lipophilic contaminants. Currently, European countries are developing indicators for monitoring pollutants in the marine environment and assessing the state of biodiversity, requirements under both Regional Seas Conventions and European legislation. As sentinel species for marine ecosystem and human health, marine mammals can be employed to assess bioaccumulated contaminants otherwise below current analytical detection limits in water and lower trophic level marine biota. To aid the development of Regional Seas marine mammal contaminants indicators, as well as Member States obligations under descriptor 8 of the EU Marine Strategy Framework Directive, the current study aims to further develop appropriate methodological standards using data collected by the established UK marine mammal pollutant monitoring programme (1990 to 2017) to assess the trends and status of PCBs in harbour porpoises. Within this case study, temporal trends of PCB blubber concentration in juvenile harbour porpoises were analysed using multiple linear regression models and toxicity thresholds for the onset of physiological (reproductive and immunological) endpoints were applied to all sex-maturity groups. Mean PCB blubber concentrations were observed to decline in all harbour porpoise Assessment Units and OSPAR Assessment Areas in UK waters. However, a high proportion of animals were exposed to concentrations deemed to be a toxicological threat, though the relative proportion declined in most Assessment Units/Areas over the last 10 years of the assessment. Recommendations were made for improving the quality of the assessment going forward, including detailing monitoring requirements for the successful implementation of such an indicator.

Prophossi: automating expert validation of phosphopeptide-spectrum matches from tandem mass spectrometry.

MOTIVATION: Complex patterns of protein phosphorylation mediate many cellular processes. Tandem mass spectrometry (MS/MS) is a powerful tool for identifying these post-translational modifications. In high-throughput experiments, mass spectrometry database search engines, such as MASCOT provide a ranked list of peptide identifications based on hundreds of thousands of MS/MS spectra obtained in a mass spectrometry experiment. These search results are not in themselves sufficient for confident assignment of phosphorylation sites as identification of characteristic mass differences requires time-consuming manual assessment of the spectra by an experienced analyst. The time required for manual assessment has previously rendered high-throughput confident assignment of phosphorylation sites challenging. RESULTS: We have developed a knowledge base of criteria, which replicate expert assessment, allowing more than half of cases to be automatically validated and site assignments verified with a high degree of confidence. This was assessed by comparing automated spectral interpretation with careful manual examination of the assignments for 501 peptides above the 1% false discovery rate (FDR) threshold corresponding to 259 putative phosphorylation sites in 74 proteins of the Trypanosoma brucei proteome. Despite this stringent approach, we are able to validate 80 of the 91 phosphorylation sites (88%) positively identified by manual examination of the spectra used for the MASCOT searches with a FDR < 15%. CONCLUSIONS: High-throughput computational analysis can provide a viable second stage validation of primary mass spectrometry database search results. Such validation gives rapid access to a systems level overview of protein phosphorylation in the experiment under investigation. AVAILABILITY: A GPL licensed software implementation in Perl for analysis and spectrum annotation is available in the supplementary material and a web server can be assessed online at http://www.compbio.dundee.ac.uk/prophossi.

Recent developments in trace analysis of poly- and perfluoroalkyl substances.

Recent developments, improvements, and trends in the ultra-trace determination of per- and polyfluoroalkyl substances (PFASs) in environmental and human samples are highlighted and the remaining challenges and uncertainties are outlined and discussed. Understanding the analytical implications of such things as adsorption of PFASs to surfaces, effects of differing matrices, varying PFAS isomer response factors, potential bias effects of sampling, sample preparation, and analysis is critical to measuring highly fluorinated compounds at trace levels. These intricate analytical issues and the potential consequences of ignoring to deal with them correctly are discussed and documented with examples. Isomer-specific analysis and the development of robust multi-chemical methods are identified as topical trends in method development for an ever-increasing number of PFASs of environmental and human interest. Ultimately, the state-of-the-art of current analytical method accuracy is discussed on the basis of results from interlaboratory comparison studies.

The phosphoproteome of bloodstream form Trypanosoma brucei, causative agent of African sleeping sickness.

The protozoan parasite Trypanosoma brucei is the causative agent of human African sleeping sickness and related animal diseases, and it has over 170 predicted protein kinases. Protein phosphorylation is a key regulatory mechanism for cellular function that, thus far, has been studied in T.brucei principally through putative kinase mRNA knockdown and observation of the resulting phenotype. However, despite the relatively large kinome of this organism and the demonstrated essentiality of several T. brucei kinases, very few specific phosphorylation sites have been determined in this organism. Using a gel-free, phosphopeptide enrichment-based proteomics approach we performed the first large scale phosphorylation site analyses for T.brucei. Serine, threonine, and tyrosine phosphorylation sites were determined for a cytosolic protein fraction of the bloodstream form of the parasite, resulting in the identification of 491 phosphoproteins based on the identification of 852 unique phosphopeptides and 1204 phosphorylation sites. The phosphoproteins detected in this study are predicted from their genome annotations to participate in a wide variety of biological processes, including signal transduction, processing of DNA and RNA, protein synthesis, and degradation and to a minor extent in metabolic pathways. The analysis of phosphopeptides and phosphorylation sites was facilitated by in-house developed software, and this automated approach was validated by manual annotation of spectra of the kinase subset of proteins. Analysis of the cytosolic bloodstream form T. brucei kinome revealed the presence of 44 phosphorylated protein kinases in our data set that could be classified into the major eukaryotic protein kinase groups by applying a multilevel hidden Markov model library of the kinase catalytic domain. Identification of the kinase phosphorylation sites showed conserved phosphorylation sequence motifs in several kinase activation segments, supporting the view that phosphorylation-based signaling is a general and fundamental regulatory process that extends to this highly divergent lower eukaryote.

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.

Polychlorinated biphenyls are associated with reduced testes weights in harbour porpoises (Phocoena phocoena).

Polychlorinated biphenyls (PCBs) are highly toxic and persistent aquatic pollutants that are known to bioaccumulate in a variety of marine mammals. They have been associated with reduced recruitment rates and population declines in multiple species. Evidence to date documents effects of PCB exposures on female reproduction, but few studies have investigated whether PCB exposure impacts male fertility. Using blubber tissue samples of 99 adult and 168 juvenile UK-stranded harbour porpoises (Phocoena phocoena) collected between 1991 and 2017, here we show that PCBs exposures are associated with reduced testes weights in adults with good body condition. In animals with poor body condition, however, the impact of PCBs on testes weights was reduced, conceivably due to testes weights being limited by nutritional stress. This is the first study to investigate the relationship between PCB contaminant burden and testes weights in cetaceans and represents a substantial advance in our understanding of the relationship between PCB exposures and male reproductive biology in cetaceans. As testes weight is a strong indicator of male fertility in seasonally breeding mammals, we suggest the inclusion of such effects in population level impact assessments involving PCB exposures. Given the re-emergent PCB threat our findings are globally significant, with potentially serious implications for long-lived mammals. We show that more effective PCB controls could have a substantial impact on the reproductive health of coastal cetacean species and that management actions may need to be escalated to ensure adequate protection of the most vulnerable cetacean populations.

The Jpred 3 secondary structure prediction server.

Jpred (http://www.compbio.dundee.ac.uk/jpred) is a secondary structure prediction server powered by the Jnet algorithm. Jpred performs over 1000 predictions per week for users in more than 50 countries. The recently updated Jnet algorithm provides a three-state (alpha-helix, beta-strand and coil) prediction of secondary structure at an accuracy of 81.5%. Given either a single protein sequence or a multiple sequence alignment, Jpred derives alignment profiles from which predictions of secondary structure and solvent accessibility are made. The predictions are presented as coloured HTML, plain text, PostScript, PDF and via the Jalview alignment editor to allow flexibility in viewing and applying the data. The new Jpred 3 server includes significant usability improvements that include clearer feedback of the progress or failure of submitted requests. Functional improvements include batch submission of sequences, summary results via email and updates to the search databases. A new software pipeline will enable Jnet/Jpred to continue to be updated in sync with major updates to SCOP and UniProt and so ensures that Jpred 3 will maintain high-accuracy predictions.

Screening for PFOS and PFOA in European air using passive samplers.

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been widely detected in the environment and in wildlife, including biota in remote areas, such as the Arctic. A monitoring programme to measure these two compounds in the atmosphere simultaneously at many sites using traditional sampling techniques (active air sampler) would be difficult to achieve. This study presents the results of using polyurethane foam-based passive air samplers (PUF-PASs) to sample ionic perfluoroalkyl sulfonates (PFASs) in three different areas: northwest of England (15 sites), UK-Norway transect (11 sites) and European survey (23 sites), for 2-3 months of exposure. Only PFOA and PFOS were regularly detected in the samplers. PFOA (200-27 000 pg per sample per day) and PFOS (1.5-720 pg per sample per day) levels present in samplers deployed in northwest of England were estimated in this study. In the UK-Norway transect campaign, only the UK samples were found to contain PFOA (100-1200 pg per sample per day) and PFOS (2.7-7.7 pg per sample per day). It was difficult to see clear distribution trends of PFOA (4.7-540 pg per sample per day) and PFOS (1.9-69 pg per sample per day) in the EU survey. However, PFOA appeared relatively elevated in samples taken close to the coastline of the North Sea. This study gives some encouragement to the idea that PUF-PAS can be used to sample PFASs. From our knowledge, this is the first study using untreated PUF disks to sample ionic PFASs in the atmosphere.

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.

Juvenile harbor porpoises in the UK are exposed to a more neurotoxic mixture of polychlorinated biphenyls than adults.

Polychlorinated biphenyls (PCBs) are a group of 209 persistent and bio-accumulative toxic pollutants present as complex mixtures in human and animal tissues. Harbor porpoises accumulate some of the highest levels of PCBs because they are long-lived mammals that feed at a high trophic level. Studies typically use the sum of a suite of individual chlorobiphenyl congeners (CBs) to investigate PCBs in wildlife. However, toxic effects and thresholds of CB congeners differ, therefore population health risks of exposure may be under or over-estimated dependent on the congener profiles present. In this study, we found congener profiles varied with age, sex and location, particularly between adult females and juveniles. We found that adult females had the highest proportions of octa-chlorinated congeners whilst juveniles had the highest proportions of tri- and tetra-chlorinated congeners. This is likely to be a consequence of pollutant offloading between mothers and calves during lactation. Analysis of the individual congener toxicities found that juveniles were exposed to a more neurotoxic CB mixture at a time when they were most vulnerable to its effects. These findings are an important contribution towards our understanding of variation in congener profiles and the potential effects and threats of PCB exposure in cetaceans.

Treatment of chronic non-malignant pain in the elderly: safety considerations.

Non-malignant pain in the elderly is frequently under-treated, with physicians appearing to be uncertain concerning how best to achieve optimum management of this common problem in individual cases. The aim of this review is to provide a brief overview and discuss the variety of interacting factors that contribute to the continuing under-treatment of chronic non-malignant pain in the older population. The central objective is to encourage safer and more effective pain management in a population that is highly vulnerable to painful conditions and to the consequences of poorly treated pain. Under-treatment of pain as experienced by the elderly is largely a consequence of uncertainties that arise within a complex environment that is underscored and exacerbated by the progressive and rapid aging of the global population. Uncertainties include the optimum management of pain in geriatric syndromes, frailty and dementia, and their impact on diagnosis, pain assessment and choices of treatment modalities. There is an inadequate evidence base for pharmacological interventions in older persons with respect to pharmacokinetic and pharmacodynamic changes that occur with aging. In this review, the prevalence of chronic pain and the incidence of adverse drug reactions are identified as factors that encourage conservatism in prescribing, as are major predictors of adverse drug reactions, i.e. aging, inappropriate combinations of medications and polypharmacy. The major classes of analgesic drugs are summarized with reference to their mechanisms of action, analgesic properties and known adverse effects. Although all medications have associated risks, the use of analgesics in managing persistent pain in elderly people is widely supported and guided on the basis of clinical experience and consensus among specialists in geriatrics and pain management. It is concluded that the absence of trial data, specific to the elderly, is substantially offset by information based on clinical experience and expert consensus statements. Used appropriately, analgesic and adjuvant treatments can and should be employed to relieve persistent pain in the expanding elderly population.

A study of aerosol entrapment and the influence of wind speed, chamber design and foam density on polyurethane foam passive air samplers used for persistent organic pollutants.

Polyurethane foam disks are a cheap and versatile tool for sampling persistent organic pollutants (POPs) from the air in ambient, occupational and indoor settings. This study provides important background information on the ways in which the performance of these commonly used passive air samplers may be influenced by the key environmental variables of wind speed and aerosol entrapment. Studies were performed in the field, a wind tunnel and with microscopy techniques, to investigate deployment conditions and foam density influence on gas phase sampling rates (not obtained in this study) and aerosol trapping. The study showed: wind speed inside the sampler is greater on the upper side of the sampling disk than the lower side and tethered samplers have higher wind speeds across the upper and lower surfaces of the foam disk at a wind speed > or = 4 m/s; particles are trapped on the foam surface and within the body of the foam disk; fine (<1 um) particles can form clusters of larger size inside the foam matrix. Whilst primarily designed to sample gas phase POPs, entrapment of particles ensures some 'sampling' of particle bound POPs species, such as higher molecular weight PAHs and PCDD/Fs. Further work is required to investigate how quantitative such entrapment or 'sampling' is under different ambient conditions, and with different aerosol sizes and types.

Field calibration of polyurethane foam disk passive air samplers for PBDEs.

A field study was performed to derive uptake rates of airborne polybrominated diphenyl ethers (PBDEs) to polyurethane foam (PUF) disk passive air samplers (PAS) and to investigate the influence of deployment location and device design. Data are presented on the gas-particle partitioning of PBDEs, since atmospheric phase distribution was considered to be a variable which could affect sampler performance. Uptake rates for these compounds were similar to those derived previously for other classes of persistent organic pollutants (POPs) (approximately 2-6 m(3)/day), with rates higher for the higher brominated species. Whilst other compound classes (e.g. polychlorinated biphenyls) are predominantly present in the air in the gas phase, heavier PBDEs have an association with particulates in the atmosphere at ambient temperatures. In this study, the PUF disk PAS therefore sampled PBDEs present in the gas phase and on fine aerosols with a similar sampling efficiency to those which are predominantly gas phase compounds. Compounds which are exclusively on particles are sampled less efficiently. A comparison of the three most commonly used PUF deployment configurations, used by different research groups, indicated little difference in uptake rates. The ranges of derived air concentrations for BDE-47, -99, and -183 between three sampler designs were 7.5-9.8, 7.4-12.4, and 4.7-6.6 pg/m(3), respectively. This suggests the robustness of this sampler in comparisons between regional and global campaigns where these three designs are employed.

Linking organochlorine contaminants with demographic parameters in free-ranging common bottlenose dolphins from the northern Adriatic Sea.

Marine top predators, including marine mammals, are known to bio-accumulate persistent pollutants such as polychlorinated biphenyls (PCBs), a serious conservation concern for these species. Although PCBs declined in European seas since the 1970s-1980s ban, considerable levels still persist in European and Mediterranean waters. In cetaceans, stranded animals are a valuable source of samples for pollutant studies, but may introduce both known and unknown biases. Biopsy samples from live, free-ranging cetaceans offer a better alternative for evaluating toxicological burdens of populations, especially when linked to known histories of identified individuals. We evaluated PCB and other organochlorine contaminants in free-ranging common bottlenose dolphins (Tursiops truncatus) from the Gulf of Trieste (northern Adriatic Sea), one of the most human-impacted areas in the Mediterranean Sea. Biopsies were collected from 32 male and female dolphins during 2011-2017. All animals were photo-identified and are part of a well-known population of about 150 individuals monitored since 2002. We tested for the effects of sex, parity and social group membership on contaminant concentrations. Males had significantly higher organochlorine concentrations than females, suggesting offloading from reproducing females to their offspring via gestation and/or lactation. Furthermore, nulliparous females had substantially higher concentrations than parous ones, providing further support for maternal offloading of contaminants. Overall, 87.5% of dolphins had PCB concentrations above the toxicity threshold for physiological effects in experimental marine mammal studies (9 mg/kg lw), while 65.6% had concentrations above the highest threshold published for marine mammals based on reproductive impairment in ringed seals (41 mg/kg lw). The potential population-level effects of such high contaminant levels are of concern particularly in combination with other known or suspected threats to this population. We demonstrate the utility of combining contaminant data with demographic parameters such as sex, reproductive output, etc., resulting from long-term studies.