Levels and Endocrine Disruptive Effects of Legacy Pops and Their Metabolites in Long-Finned Pilot Whales of the Faroe Islands
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Doctoral theses at NTNU, 2017:279 Katrin S. Ho Katrin S. Hoydal ydal Levels and endocrine disruptive oral thesis oral effects of legacy POPs and their metabolites in long-finned pilot Doct whales of the Faroe Islands ISBN 978-82-326-2626-7 (printed ver.) ISBN 978-82-326-2627-4 (electronic ver.) ISSN 1503-8181 Doctoral theses at NTNU, 2017:279 NTNU Philosophiae Doctor Philosophiae Department of Biology Thesis for the Degree of the Degree Thesis for Faculty of Natural Sciences of Natural Faculty egian University of Science and Technology of Science egian University Norw Katrin S. Hoydal Levels and endocrine disruptive effects of legacy POPs and their metabolites in long-finned pilot whales of the Faroe Islands Thesis for the Degree of Philosophiae Doctor Trondheim, October 2017 Norwegian University of Science and Technology Faculty of Natural Sciences Department of Biology NTNU Norwegian University of Science and Technology Thesis for the Degree of Philosophiae Doctor Faculty of Natural Sciences Department of Biology © Katrin S. Hoydal ISBN 978-82-326-2626-7 (printed ver.) ISBN 978-82-326-2627-4 (electronic ver.) ISSN 1503-8181 Doctoral theses at NTNU, 2017:279 Printed by NTNU Grafisk senter Acknowledgements This study was carried out as a PhD project at the Norwegian University of Science and Technology (NTNU) in Trondheim, Norway, where most of the analyses were performed. Additionally, analyses have been performed at the University of Barcelona (UB) and the University of Copenhagen (KU), as well as the samples have been sent to Natural Wildlife Research Centre, Carleton University, Ottawa, Canada for analysis of contaminants. The study was funded by the Faroese Research Council and the Environment Agency on the Faroe Islands. The work has thus involved many collaborations and help from people whom I greatly wish to acknowledge: I would like to thank Maria Dam from the Environment Agency for helping with the initiation of this project and for establishing the contacts to NTNU, and also for putting time and effort in to the project and co-authoring the manuscripts. I am also grateful for the very generous working conditions that I have had at the Environment Agency, during the whole process of working with this project. I also warmly wish thank to my supervisors at NTNU, my main supervisor Bjørn Munro Jenssen and my co-supervisor Augustine Arukwe, for making it possible for me to come and do this project at the Biological department at NTNU and carry out the analyses at their laboratories, and to always welcomingly accommodating me at the department on my longer and shorter stays in Trondheim. I am very grateful to Bjørn for the positive engagement towards the project and the outcome of it, and for the good guidance and valuable comments and suggestions during the writing of the papers and this thesis, and to Augustine for the large engagement and efforts in the analyses work and in the interpretation of the results. Similarly, I wish to thank my external co-supervisors, Asunción (Xon) Borrell at UB and Bjarne Styrishave at KU for welcoming me to their laboratories in Barcelona and Copenhagen to carry out analyses, and for putting much effort in the laboratory work and interpretation of the results. In addition, I wish to thank Xon, and also Alex Aguilar from UB, for giving me a warm welcome and help during my stay in Barcelona. Tomasz (Tomek) Ciesielski at NTNU I want to thank for all the help and engagement in the vitamin analyses and statistical analyses, and for teaching me to use SIMCA. Also for establishing a collaboration with Andrzej Wasik at the Gdansk University of Technology, who is also greatly acknowledged for performing some of the vitamin analyses. My other co-authors I also wish to thank for their participation in this study: Robert Letcher for taking care of the POP analyses at the Carleton University in Canada and for the valuable comments to the papers, David Blair for carrying out the analyses of POPs and metabolites, and Christina Lockyer for carrying out the age analyses. At NTNU I wish to thank Grethe S. Eggen, Marianne Olufsen, Randi Røsbak and Gunnhild Olsen, and at KU Kenneth M. Pedersen for their great help with the laboratory analyses and together with the other people at NTNU, KU and UB for making the laboratory work and my stays such nice times. I wish to thank Maria Dam, Tahti Oksanen, Thea Dam, Emilia Dam, Sanna T. Nielsen, Niels J. Nielsen, Sjúrður Hammer, Mathias Kirkegaard, Mette Kibsgaard and Lars Mehling, as well as Bjarni Mikkelsen and Høgni Arnbjarnarson for help with the sampling at the two sample occasions in Tórshavn and Vestmanna. Maria and Sanna deserve special thanks for all the help and the additional work on the sample preparation in connection with the sampling events. I am also grateful to my colleagues at the Environment Agency during these years, and in particular, I wish to thank Birgitta Andreasen for reading through this thesis. Finally, I wish to thank my lovely family, my husband Einar and our children, Gunnvør, Rúna, Bjørg and Kjartan, for their patience and support during this long time, when I have been abroad for long time-periods, and especially during this last part when the project largely has affected our family life. I also wish to thank the rest of my family, my mother, sisters and brother and my "1/(?/ '#&5 for their great support and practical help during these busy years with much travelling. I want to dedicate this thesis to my beloved father Kjartan Hoydal, who passed away in May of 2016. 1 Contents Abstract ................................................................................................................................................... 4 List of papers ........................................................................................................................................... 6 Declaration of contributions ................................................................................................................... 6 1 Introduction .................................................................................................................................... 7 1.1 Background ............................................................................................................................. 7 1.2 Pilot whales ............................................................................................................................. 8 1.3 POPs: PCBs, OCPs, and PBDEs ................................................................................................. 9 1.3.1 Metabolism of POPs ...................................................................................................... 11 1.4 Endocrine distrupting effects of POPs .................................................................................. 12 1.4.1 Steroid hormones ......................................................................................................... 12 1.4.2 Thyroid hormones ......................................................................................................... 13 1.4.3 Vitamin A, E and D......................................................................................................... 14 1.5 POP exposure in pilot whales................................................................................................ 15 1.6 Aim of the study .................................................................................................................... 16 2 Methods ........................................................................................................................................ 17 2.1 Sampling ................................................................................................................................ 17 2.2 Division into age/sex groups ................................................................................................. 18 2.3 Analysis of contaminants ...................................................................................................... 19 2.4 Analysis of phase I and phase II enzyme induction............................................................... 19 2.5 Analysis of thyroid hormones ............................................................................................... 19 2.6 Analysis of vitamins in liver and plasma ............................................................................... 20 2.7 Analysis of steroid hormones................................................................................................ 20 2.8 Statistical analyses ................................................................................................................ 20 3 Results and Discussion: ................................................................................................................. 21 3.1 POP concentrations and maternal transfer .......................................................................... 21 3.2 CYP enzyme induction and POP metabolism ........................................................................ 23 3.2.1 Metabolite concentrations and distribution ................................................................. 27 3.3 Endocrine disruptive effects ................................................................................................. 28 3.3.1 Steroid hormones ......................................................................................................... 28 3.3.2 Thyroid hormones ........................................................................................................