In Sediment, and Fate of Organic Contaminants in Dragonfly Larvae (Aeshnidae) from Highway Sedimentation Ponds and Natural Ponds
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Source Origin of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediment, and Fate of Organic Contaminants in Dragonfly Larvae (Aeshnidae) from Highway Sedimentation Ponds and Natural Ponds Viviane Girardin Master Thesis in Toxicology Department of Biosciences Faculty of Mathematics and Natural Sciences UNIVERSITY OF OSLO November 2018 © Viviane Girardin 2018 Source Origin of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediment, and Fate of Organic Contaminants in Dragonfly Larvae (Aeshnidae) from Highway Sedimentation Ponds and Natural Ponds Viviane Girardin http://www.duo.uio.no/ Print: Reprosentralen, Universitetet i Oslo II Acknowledgements The presented thesis was carried out at the Department of Biosciences at the University in Oslo, and is associated with the project Reducing Highway Runoff Pollution (REHIRUP). The project invests in research and development with the goal of presenting optimal solutions for design, operation and maintenance of runoff treatment. REHIRUP is a joint collaboration between the Norwegian Public Roads Administration (NPRA), Swedish Transport Administration, and the Danish Road Directorate. The Norwegian Institute for Water Research (NIVA) is a partner in part of the project. I would like to thank my supervisors, Professors Merete Grung, Sondre Meland, and Katrine Borgå for their help and support. I would like to express my gratitude to Sondre for going above and beyond in his role as a supervisor, being always available to answer my questions, and for the extra help with statistics. Merete for all her help in the lab and for several constructive feedbacks. A huge thank you to my mentors Kjersti Kronvall and Lene Sørlie Heier from the Norwegian Public Roads Administration for their tremendous support, and for sharing their knowledge with me. Thank you Alfhild Kringstad and Katharina Løken, and many others from NIVA for the great help and patience in and out of the lab. Professors Ketil Hylland and Tom Andersen for always being very welcoming whenever I asked for advice. Amalie Liane for the tips, for showing me the way to the ponds, and for the material you left for me when you were done. Sofie Lindman, my dear field buddy, for the company in so many field trips, and whom inspired me to be a more organized person. Øyvind Grotmol for his patience and time checking my statistics. Clare McEnally, Patricia Decourt, and Mariana Paz for helping me during many field trips. Thank you so much for proofreading (a thousand times) this thesis, and the amazing support Clare! Thank you Pati, “bestifrendi”, for turning what it would have been the worse field trip into the funniest, most memorable of them all. And an extra round of applause for Mariana, who not only proved to be an amazing larva whisperer, but also took such good care of my kids, becoming my daughter’s idol. And my family: My daughter and son, Helena and Johan, thank you for your patience and love. I could not have asked for better kids. I love you! (You guys could have slept through the night, and made less of a mess at home, but ok). My awesome mom! Thank you for III absolutely everything! And last, but not least; Thank you Joachim for being there for me. For your patience, solicited and unsolicited advices, support, and love. I love you! I am now ready for a 48hr nap… Figure 1 - Thank you all! IV Abstract Road and tunnel wash runoff contain a mixture of organic and inorganic contaminants that threatens the quality of natural water bodies, and the health of the organisms dependent on these waters. A variety of treatment solutions can be established to reduce potential runoff impact. The most common mitigation adopted in Norway is the installation of nature-based sedimentation ponds. A variety of organisms migrate to these ponds over time, and are thus at risk of exposure to high levels of traffic-related contaminants. Dragonflies, with their aquatic life stage, can potentially transfer these substances back to the terrestrial environment. This aim of this study was to assess the source origin and fate of polycyclic aromatic hydrocarbons (PAHs), and two types of organobromine compounds used as flame retardants, polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in three natural and seven highway sedimentation ponds in Norway. Sediment samples were used to determine source origin of PAHs. The concentrations of organic contaminants were analyzed in dragonfly larvae to investigate their potential role as pollutant vectors across ecosystems. Parent and alkylated PAHs in sediment were measured, and the results were used to characterize the source of PAHs. Distribution patterns of selected PAHs showed similar patterns in all sedimentation ponds, and distinct patterns in natural ponds. Specific PAH ratios indicated that sedimentation ponds are dominated by petrogenic PAHs, whereas natural ponds showed pyrogenic dominance. Moreover, the addition of alkylated PAHs resulted in significant changes in the environmental quality standard values related to sediment pollution. PAHs, PBDEs and HBCD were quantified in sediment, and larval exuvia and tissue. Haemolymph was also analyzed for PAH metabolites. The results indicated that dragonfly larvae accumulate PAHs in the exuvia, but not sufficiently enough to avoid bioaccumulation. 1-hydroxypyrene was detected only in some of the samples and at very low concentrations, and thus it is not clear whether larvae are able to metabolize PAHs at low levels or if the metabolite has come from others sources. Nevertheless, the results suggest that metabolites are not suitable biomarkers for PAH exposure in dragonfly larvae. Levels of BFRs were detected at very low concentrations, and the results were qualified. Overall, there was no indication of bioaccumulation of BFRs. V Abbreviations AADT Annual Average Daily Traffic ACE Acenaphthene ACY Acenaphthylene ANTH Anthracene BaA Benzo[a]anthracene BaP Benzo[a]pyrene BbjF Benzo[b,j]fluoranthene BeP Benzo[e]pyrene BFR Brominated Flame Retardants BghiPER Benzo[ghi]perylene BkF Benzo[k]fluoranthene CAS Chemical Abstracts Service CHR Chrysene DachA Dibenz[ac/ah]antracene DIB Dibenzothiophene FLO Fluorene FLUORA Fluoranthene GC/MS Gas chromatography/Mass spectrometry GPC Gel Permeation Chromatography VI HBCD Hexabromocyclododecane HMW High Molecular Weight HPLC High Performance Liquid Chromatography I123P Indeno [1,2,3-cd]pyrene IS Internal Standard LMW Low Molecular Weight NAPH Napthalene NIVA Norwegian Institute for Water Research NPRA Norwegian Public Roads Admnistration PAH Polycyclic Aromatic Hydrocarbon PBDE Polybrominated Diphenyl Ethers PER Perylene PHEN Phenanthrene PYR Pyrene RBSP River Basin-Specific Pollutants SRM Standard Reference Material WFD Water Framework Directive VII VIII Table of Contents Abstract ..................................................................................................................................... V Table of Contents ..................................................................................................................... IX 1 Introduction ........................................................................................................................ 1 1.1 Odonata – Dragonflies ................................................................................................. 4 1.1.1 Dragonflies as model organisms .......................................................................... 5 1.1.2 Life cycle .............................................................................................................. 5 1.2 Polycyclic aromatic hydrocarbons (PAHs) ................................................................. 6 1.2.1 PAH metabolites .................................................................................................. 9 1.3 Brominated flame retardants (BFRs) ......................................................................... 10 1.4 Sedimentation ponds .................................................................................................. 11 1.5 Objectives .................................................................................................................. 14 2 Materials and methods ..................................................................................................... 15 2.1 Study sites .................................................................................................................. 15 2.1.1 Sedimentation ponds .......................................................................................... 17 2.1.2 Reference ponds ................................................................................................. 20 2.2 Sampling .................................................................................................................... 21 2.3 Laboratory ................................................................................................................. 22 2.3.1 Dragonfly Larvae ............................................................................................... 22 2.3.2 Extraction method .............................................................................................. 25 2.3.3 PAH metabolites ................................................................................................ 26 2.3.4 Analysis .............................................................................................................. 27 2.3.5 Quality Assurance .............................................................................................. 27 2.4 Experimental