Analysis of flame retardants in marine organisms of Antarctic: Evaluation of long-range transport of these emerging pollutants. MÀSTER Treball realitzat per: Xuefei Yang Dirigit per: Dr. Ethel Eljarrat Esebag Dr. Alejandro Josa Garcia-Tornel Màster en: Ingeniería Ambiental Barcelona, 23 de junio del 2016 Departament d. Ingeniería Civil i Ambiental. I TREBALL FINAL DE TREBALL FINAL DEPOSIT DATE: June of 2016 ABSTRACT Persistent organic pollutants (POPs) are toxic chemicals that adversely affect human health and the environment around the world. The Stockholm Convention defined four criteria of POPs for persistence, bioaccumulation, potential for long-range transport and toxicity. Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) are the most used flame retardants (FRs) that are POPs regulated under the Stockholm Convention. Their production has been banned in Europe and North America. Hence new brominated FRs (BFRs) are used as substitutes; as well as chlorinated FRs, such as dechloranes. Over the years, presence of POPs has been detected in remote areas like Arctic and Antarctic. Although there are very few human impacts because of the geographic isolation and extreme climate, researches have demonstrated that POPs have reached this isolated continent and ocean area unfortunately. The present study investigates the occurrence of PBDEs, emerging BFRs and dechloranes in a total of 31 samples of 2 species of seals (Mirounga leonina and Arctocephalus gazella) collected in Livingston Island and Penguin Island (Antarctica). The samples correspond to different tissues: muscle, nervous system, fat and fur. The main aims of this study are: 1) to detect the presence of emerging FRs in these samples which can prove the transport capacity of long range with risks to the environment and living beings; 2) to assess the degree of exposure of these seals in this area with the levels of FRs found and compare them with other studies published in areas of the Antarctic. PBDEs, dechloranes and HBCDs were detected in some samples with the same order of magnitude (low ng/g lipid weight (lw)). In terms of examined PBDEs, BDE-28 and BDE-47 were the predominant pollutants in fat and fins samples with lower concentrations comparing with previous studies. As for dechloranes, Dec 602 showed the presence in fins, fat and nervous system samples while anti-DP was only detected in fat samples. In the case of HBCD, only γ-HBCD was found in fat samples. These results showed that Dec 602 and anti-DP, as well as PBDEs and HBCD, have the ability to be transported to long distance. II ACKNOWLEDGEMENTS First of all, I would like to acknowledge my tutor in IDAEA-CSIC, Dr. Ethel Eljarrat Esebag, for her professionalism and for giving me the opportunity to make this TFM in her consulting by giving me all the help and information that I needed, and for the time she dedicated. I also want to extend my gratitude to my tutor of UPC, Dr. Alejandro Josa Garcia- Tornel, for his support and guidance during the thesis. And I want to thank Institute of IDAEA-CSIC for giving me the chance to finish my master thesis there and providing all I have needed during the experimental process. I wish to thank IDAEA scientists and staff for their friendship and support, specially to Òscar Aznar-Alemany for his guidance and patience during the experiment. I wish to thank all my friends from the Master because without your kindness and support, these two years could not have passed so enjoyably. Finally, my deepest appreciation goes to my family in China and my love for their infinite and unconditional love, encouragement and support. THANK YOU ALL SO MUCH! III NOMENCLATURE ASPA Antarctic Specially Protected Area ASE accelerated solvent extraction BBB blood – brain barrier BFR brominated flame retardant BSEF Bromine Science Environmental Forum DBDPE decabromodiphenyl ethane Dec 602 dechlorane 602 Dec 603 dechlorane 603 Dec 604 dechlorane 604 deca-BDE decabrominated diphenyl ether DP dechlorane plus ECHA European Chemicals Agency EFSA European Food Safety Authority EPA Environmental Protection Agency EU European Union FR flame retardant GC gas chromatography HBB hexabromobenzene HBCD hexabromocyclododecane hepta-BDE heptabrominated diphenyl ether hexa-BDE hexabrominated diphenyl ether HFR halogenated flame retardant HPLC high-performance liquid chromatography LC liquid chromatography LOD limit of detection LPV low production volume LOQ limit of quantification lw lipid weight MeO-PBDE methoxylated polybrominated diphenyl ether MS mass spectrometry IV MS/MS tandem mass spectrometry nona-BDE nonabrominated diphenyl ether NS nervous system octa-BDE octabrominated diphenyl ether PBDE polybrominated diphenyl ether PBEB pentabromoethylbenzene PCB polychlorinated biphenyl penta-BDE pentabrominated diphenyl ether PLE pressured liquid extraction POPs Persistent Organic Pollutants REACH Registration, Evaluation, Authorisation and Restriction of Chemicals SPE solid phase extraction SRM selected reaction monitoring TBBPA tetrabromobisphenol A tetra-BDE tetrabrominated diphenyl ether VCCEP Voluntary Children's Chemical Evaluation Program V TABLE OF CONTENTS ABSTRACT ................................................................................................................................ II ACKNOWLEDGEMENTS ...................................................................................................... III NOMENCLATURE .................................................................................................................. IV TABLE OF CONTENTS .......................................................................................................... VI CHAPTER 1 INTRODUCTION ............................................................................................... 1 1. Persistent organic pollutants ...................................................................................... 1 1.1. General characteristics of POPs ............................................................................ 1 1.2. Stockholm Convention on POPs ............................................................................ 1 2. Flame retardants ......................................................................................................... 3 2.1. FRs legislated in Stockholm Convention ............................................................... 4 2.2. Alternatives of restricted FRs ................................................................................ 7 3. Natural compounds (MeO-PBDEs) ........................................................................... 9 4. Presence of FRs in remote environment .................................................................. 10 4.1. Presence of PBDEs in remote environment ........................................................ 10 4.2. Presence of dechloranes in remote environment ................................................ 19 CHAPTER 2 OBJECTIVES AND METHODS ..................................................................... 20 1. Objectives ................................................................................................................... 20 2. Study Area* ............................................................................................................... 21 2.1. Livingston Island ................................................................................................... 21 2.2. Penguin Island ....................................................................................................... 22 3. Sampling ..................................................................................................................... 23 4. Materials and methods .............................................................................................. 25 4.1. Solvents, patterns, material and equipment ........................................................ 25 4.2. Sample preparation ............................................................................................... 26 4.3. Instrumental analysis ............................................................................................ 27 4.4. Analytical parameters ........................................................................................... 33 CHAPTER 3 RESULTS AND DISCUSSION ........................................................................ 34 1 PBDEs, MeO-PBDEs and NFRs in samples ........................................................... 34 2. Dechloranes in samples ............................................................................................. 38 2 HBCD in samples ...................................................................................................... 42 CHAPTER 4 CONCLUSION .................................................................................................. 44 VI REFERENCES .......................................................................................................................... 45 ANNEX....................................................................................................................................... 56 VII CHAPTER 1 INTRODUCTION 1. Persistent organic pollutants 1.1. General characteristics of POPs Persistent organic pollutants (POPs) are organic compounds that persist in the environment, bioaccumulate through the food web, and pose a risk of causing adverse effects to human health and the environment. This group of priority pollutants consists of pesticides (such as DDT), industrial chemicals (such