Multi-residue enantioselective determination of emerging drug contaminants in seawater by solid phase extraction and liquid chromatography-tandem mass spectrometry.

This study proposes a new multi-residue enantioselective method for the determination of emerging drug contaminants in sea water by solid phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). To achieve satisfactory enantiomeric separation with a vancomycin stationary phase it was essential to limit sodium chloride in extracted samples to [less than] 1 µg injection-1. This was achieved through a straightforward SPE method using a 50 mL water wash volume and analyte elution in acetonitrile. A Chiral-V enantioselective column (150 x 2.1mm; 2.7µm particle size) operated in polar ionic mode enabled simultaneous drug separations in 30 minutes. Analytes with enantioresolution E$ were the stimulants amphetamine and methamphetamine, the beta-agonist salbutamol, the beta-blockers propranolol, sotalol and acebutolol, the anti-depressants fluoxetine, venlafaxine, desmethylvenlafaxine and citalopram, and the antihistamine chlorpheniramine. Method quantitation limits were [less than] 10 ng L-1 and method trueness was 80-110% for most analytes. The method was applied to samples from the Forth and Clyde estuaries, Scotland. Chiral drugs were present at concentrations in the range 4-159 ng L-1 and several were in non-racemic form (enantiomeric fraction G 0.50) demonstrating enantiomer enrichment. This emphasises the need for further enantiospecific drug exposure and effect studies in the marine environment

The concentration and biomagnification of trace metals and metalloids across four trophic levels in a marine food web

To be able to assess progress towards “Good Environmental Status” adopted across European Member States, and by the United Kingdom through its 3-stage Marine Strategy, contaminant concentrations and their biological effects need to be assessed in environmental samples by comparison to assessment criteria. This study examines the variability of concentrations (inter- and intra- species variation) of three priority heavy metals (Hg, Cd and Pb) and six additional trace metals and metalloids (As, Ni, Se, Zn, Cu and Cr) in twenty-three species across four trophic levels from different locations around Scotland. Trophic magnification factors (TMFs) were calculated using two methods for metals/metalloids possessing a significant trophic relationship (Hg, Cd, Cu, Ni and Zn) to refine and improve the application of TMFs to assess and predict biomagnification risk of metals/metalloids to biota in the environment. It was concluded that a reasonable balance in sample numbers of lower- versus higher-trophic level organisms is highly recommended when calculating TMFs and appropriate species selection is vital to ensure TMFs accurately represent the selected ecosystem

Understanding marine food web dynamics using fatty acid signatures and stable isotope ratios:Improving contaminant impacts assessments across trophic levels

Scotland's marine food webs support a diversity of species and habitats. They contribute to maintaining the balance of the natural environment. Previous studies show that these ecosystems are contaminated by persistent organic pollutants and trace metals; with animals in higher trophic levels (e.g. cetaceans and pinnipeds) containing concentrations that are among the highest found in the ocean. Contaminants represent one of many pressures to which species and habitats are exposed. In assessing the contribution of contaminants to the overall pressure, measuring contaminants at a specific trophic level and then using trophic magnification factors (TMFs) to estimate concentrations at other trophic levels permits assessments across the food web, as well as allowing the adjustment of contaminant concentrations to a particular trophic level for comparison to assessment criteria. Fatty acid (FA) signatures and stable isotope (SI) ratios were used to develop a picture of Scottish marine food web ecology and reliably ascribe trophic levels to a wide range of species. Fatty acid trophic markers (FATMs) were used as trophic level indicators and with SI analysis, permitted identification of the mean trophic level of each species and determination of the feeding patterns and predator-prey relationships existing in the Scottish marine food web. Two hundred and eleven (211) samples comprising of seven fish species, one shark species, fourteen marine invertebrate species, three marine mammal species and two zooplankton species from different locations around Scotland were found to have mean trophic levels ranging from 1.47 ± 0.11 in zooplankton to 5.02 ± 0.35 in harbour seal. Fatty acid profile showed specific dietary information which differed between the eleven taxonomic classes and twenty-seven species. The organic and inorganic contaminant concentrations of the species for which trophic level has been determined, together with TMFs, will be reported in future papers

The concentration and biomagnification of PCBs and PBDEs across four trophic levels in a marine food web.

Contracting Parties to the OSPAR Convention for the Protection of the Maine Environment of the North-East Atlantic are required to undertake monitoring and assessment of both inorganic and organic contaminants. There is a requirement to assess contaminants across different trophic levels on an ecosystem-specific basis. However, this is currently constrained by the availability of relevant samples to cover the full range of trophic levels. This study investigates the variability (inter- and intra-species variation) of the concentrations and distributions of thirty-two polychlorinated biphenyl (PCB) congeners and nine polybrominated diphenyl ether (PBDE) congeners in twenty-six species covering four trophic levels from different geographic locations around Scotland. Trophic magnification factors (TMFs) were calculated using a traditional method and a balanced method for both the ICES-7 PCBs and BDE47, to refine and improve the application of TMFs to assess and predict biomagnification risk to biota in the marine environment. There were clear differences in congener percentage distribution between sample categories and species, with differences influenced by physiological processes and eco-biological parameters. Trophic magnification was found to occur for the ICES-7 PCBs and BDE47 using the traditional method, with the highest degree of trophic magnification reported for CB52. An unbalanced dataset was found to influence the calculated TMF and in some cases, the overall conclusion of the trophic transfer of PCB and PBDE congeners. The balanced method is highly recommended for calculating TMFs to ensure that the TMF is a true indication of the biomagnification potential, particularly when conducting regional comparisons for which sampling requirements are difficult to achieve

Characterisation of microplastics is key for reliable data interpretation.

Microplastic research has gained attention due to the increased detection of microplastics (<5 mm size) in the aquatic environment. Most laboratory-based research of microplastics is performed using microparticles from specific suppliers with either superficial or no characterisation performed to confirm the physico-chemical information detailed by the supplier. The current study has selected 21 published adsorption studies to evaluate how the microplastics were characterised by the authors' prior experimentation. Additionally, six microplastic types described as "small" (10–25 μm) and "large" (100 μm) were commercially acquired from a single supplier. A detailed characterisation was performed using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, particle size analysis, and N2-Brunauer, Emmett and Teller adsorption-desorption surface area analysis. The size and the polymer composition of some of the material provided by the supplier was inconsistent with the analytical data obtained. FT-IR spectra of small polypropylene particles indicated either oxidation of the particles or the presence of a grafting agent which was absent in the large particles. A wide range of sizes for the small particles was observed: polyethylene (0.2–549 μm), polyethylene terephthalate (7–91 μm) and polystyrene (1–79 μm). Small polyamide (D50 75 μm) showed a greater median particle size and similar size distribution when compared to large polyamide (D50 65 μm). Moreover, small polyamide was found to be semi-crystalline, while the large polyamide displayed an amorphous form. The type of microplastic and the size of the particles are a key factor in determining the adsorption of pollutants and subsequent ingestion by aquatic organisms. Acquiring uniform particle sizes is challenging, however based on this study, characterisation of any materials used in microplastic-related experiments is critical to ensure reliable interpretation of results, thereby providing a better understanding of the potential environmental consequences of the presence of microplastics in aquatic ecosystems

Aging microplastics enhances the adsorption of pharmaceuticals in freshwater.

Plastic pollution is an increasing environmental concern. Pollutants such as microplastics (< 5 mm) and pharmaceuticals often co-exist in the aquatic environment. The current study aimed to elucidate the interaction of pharmaceuticals with microplastics and ascertain how the process of photo-oxidation of microplastics affected the adsorption of the pharmaceuticals. To this end, a mixture containing ibuprofen, carbamazepine, fluoxetine, venlafaxine and ofloxacin (16 μmol L−1 each) was placed in contact with one of six either virgin or aged microplastic types. The virgin microplastics were acquired commercially and artificially aged in the laboratory. Polypropylene, polyethylene, polyethylene terephthalate, polyamide, polystyrene and polyvinyl chloride microparticles were evaluated at two sizes, described as small (D50 < 35 μm) and large (D50 95–157 μm). Results demonstrated that the study of virgin particles may underestimate the adsorption of micropollutants onto microplastics. For virgin particles, only small microparticles of polypropylene, polyethylene, polyvinyl chloride and both sizes of polyamide adsorbed pharmaceuticals. Aging the microplastics significantly increased the adsorption of pharmaceuticals by microplastics. Fluoxetine adsorbed onto all aged microplastics, from 18% (large polyethylene terephthalate) to 99% (small polypropylene). The current investigation highlights the potential of microplastics to act as a vector for pharmaceuticals in freshwater, especially after aging

Adsorption of cyanotoxins on polypropylene and polyethylene terephthalate: microplastics as vector of eight microcystin analogues.

Plastics are utilised globally but are of environmental concern due to their persistence. The global presence of microplastics (particles <5 mm in all dimensions) in freshwater environments is increasingly reported, as has the presence of cyanobacterial toxins, including the microcystins. We elucidated the potential role of microplastics as a vector for eight microcystin analogues. Two sizes of polypropylene (PP) and polyethylene terephthalate (PET) microparticles were evaluated. The median particle size distribution (D50) was 8–28 μm for small particles, and 81–124 μm for large particles. Additionally, microcystin-LR and -LF were evaluated individually using small PP and PET to elucidate the adsorption behaviour in the absence of competition. Microcystin hydrophobicity, polymer material, and particle size were key factors influencing adsorption to the plastic microparticles. The small size PP microparticles demonstrated a high affinity for the 8 microcystin analogues. The proportion of microcystin adsorbed onto the small particles of PP after 48 h contact was between 83 and 100%, depending on the analogue. Of all analogues investigated, only microcystin-LW and -LF adsorbed onto the larger sized PP and PET microparticles. Individually, greater amounts of MC-LF adsorbed onto the small PET (19%) compared to when it was present in the mixture of microcystins (11%). While MC-LR did not adsorb onto small PET microparticles in the mixture, 5% adsorption was observed when individually in contact with small PET microparticles. The results demonstrated that microplastics can adsorb eight different microcystin analogues and that more hydrophobic analogues are more likely to adsorb than less hydrophobic analogues

Long-finned pilot whale population diversity and structure in Atlantic waters assessed through biogeochemical and genetic markers

Acknowledgements. Cetacean samples were collected under the auspices of stranding monitoring programs run by the Sociedade Portuguesa de Vida Selvagem, the Coordinadora para o Estudio dos Mamíferos Mariños (supported by the regional government Xunta de Galicia), the UK Cetacean Strandings Investigation Programme and the Scottish Agriculture College Veterinary Science Division (jointly funded by Defra and the Devolved Governments of Scotland and Wales), the Marine Mammals Research Group of the Institute of Marine Research (Norway), the Museum of Natural History of the Faroe Islands and the International Fund for Animal Welfare Marine Mammal Rescue and Research Program (USA). The authors thank all the members of these institutions and organizations for their assistance with data and sample collection. S.S.M., P.M.F. and M.F. were supported by PhD grants from the Fundação para a Ciência e Tecnologia (POPH/FSE ref SFRH/BD/ 38735/ 2007, SFRH/BD/36766/2007 and SFRH/BD/30240/ 2006, respectively). A.L. was supported by a postdoctoral grant from the Fundação para a Ciência e Tecnologia (ref SFRH/BPD/82407/2011). The work related to strandings and tissue collection in Portugal was partially supported by the SafeSea project EEAGrants PT 0039 (supported by Iceland, Liechtenstein and Norway through the EEA Financial Mechanism), the MarPro project Life09 NAT/PT/000038 (funded by the European Union program LIFE+) and the project CetSenti FCT RECI/AAG-GLO/0470/2012 (FCOMP- 01-0124-FEDER-027472) (funded by the program COMPETE and the Fundação para a Ciência e Tecnologia). G.J.P. thanks the University of Aveiro and Caixa Geral de Depósitos (Portugal) for financial support. The authors acknowledge the assistance of the chemical analysts at Marine Scotland Science with the fatty acid analysis.Peer reviewedPostprintPublisher PD

Inter-species differences in polychlorinated biphenyls patterns from five sympatric species of odontocetes : Can PCBs be used as tracers of feeding ecology?

The authors gratefully acknowledge the assistance of volunteers from the Galician (CEMMA) and Portuguese (SPVS) stranding networks. The authors would like to thank R. Gallois and C. Trichet for their participation on total lipid content analysis. P. Méndez-Fernandez was supported during the research period through a PhD grant from the Fundação do Ministério de Ciência e Tecnologia de Portugal and ANIMATE project (SFRH/BD/36766/2007) and through a Science Without Borders (CSF) young talent postdoctoral grant of the Brazilian government. G. J. Pierce acknowledges support from the EU ANIMATE project (MEXC-CT-2006-042337), University of Aveiro and Caixa Geral de Depósitos (Portugal).Peer reviewedPostprin

Assessment of the toxicological status of small cetacean species from the North West Iberian Peninsula

27th Conference of the European Cetacean Society, Interdisciplinary Approaches in the Study of Marine Mammals, 8th-10th April 2013, Setúbal, PortugalIn order to determine the contamination status and vulnerability of five of the most frequent small cetaceans from the NW Iberian Peninsula (NWIP) (common dolphin Delphinus delphis, harbour porpoise Phocoena phocoena, bottlenose dolphin Tursiops truncatus, striped dolphin Stenella coeruleoalba and long-finned pilot whale Globicephala melas), 32 congeners of polychlorinated biphenyls (PCBs) were analysed in their blubber and 14 trace elements (Ag, As, Cd, Co, Cu, Cr, Fe, Hg, Mn, Ni, Pb, Se, V, Zn) in liver and kidneyN