Source inventory of flame retardants in Sweden Does the release of flame retardants pose any danger to the environment? Henrik Karlsson Degree project in biology, Master of science (2 years), 2020 Examensarbete i biologi 30 hp till masterexamen, 2020 Biology Education Centre, Uppsala University Supervisor: Jakob Gustavsson External opponent: Lutz Ahrens Abstract ...................................................................................................................................................... 1 Use and Exposure today ........................................................................................................................... 2 Our study ................................................................................................................................................... 4 Materials and methods ............................................................................................................................. 5 Compounds ............................................................................................................................................. 5 Sampling sites and sampling ................................................................................................................ 7 Agriculture ......................................................................................................................................... 7 Airports & Stormwater .................................................................................................................... 8 Industries ........................................................................................................................................... 8 WTF (waste treatment facilities) ..................................................................................................... 8 WWTP (wastewater treatment plants) ........................................................................................... 8 Analysis ................................................................................................................................................ 12 Quality assurance/Quality control (QA/QC) .................................................................................... 13 Calculation of river fluxes .................................................................................................................. 15 Results ...................................................................................................................................................... 16 Detection frequency ............................................................................................................................ 16 Total concentration ............................................................................................................................. 17 Fluxes.................................................................................................................................................... 19 Composition profile ............................................................................................................................. 20 Toxicity ................................................................................................................................................. 22 Discussion/conclusion .............................................................................................................................. 25 Thanks ...................................................................................................................................................... 25 References ................................................................................................................................................ 26 Appendix .................................................................................................................................................. 29 Abstract The idea of controlling fires by making fire resistant materials has been around for a long time, but it was first during the industrialization that we began to develop flame retardants (FRs) in large scale. Some of the first more advanced FRs called the brominated FRs were also those who were first questioned and later banned. In the Swedish industry, the brominated substances account for less than 1% of the use since many substances are prohibited and use is regulated. In order to limit the use of hazardous chemical substances in electronics, the RoHS Directive (Restriction of the use of certain Hazardous Substances in Electrical and Electronic Equipment) was introduced. Of the 59 substances we were looking for, 34 were found in the samples. The sites that emit higher concentration of substances often have a higher complexity in the profile with both new and old substances. The purpose of this study was to investigate which new flame retardants are released into the environment and if these pose any danger to animals and humans. Although the focus is on new alternative FRs, it was also tested for legacy substances to see if these still are released to the environment and in what amount. For example, for BDE-209 which is a legacy compound the toxic concentration is considered to be about 5,000 ng/L which is a thousand times higher than our highest concentration. 1 Introduction The idea of controlling fires by making fire resistant materials has been around for a long time, but it was first during the industrialization that we began to develop flame retardants (FRs). Already in the early Chinese and Egyptian civilizations, attempts were made to prevent fire by impregnating building materials (wood) with a solution of vinegar and aluminum. A major advance in flame retardation occurred in the 1820s when Gay-Lussac began researching the subject by understanding the mechanisms and developing more effective substances. He suggested the use of ammonium phosphates and borax which are still used today (Horrocks & Price 2001). In US, the Flammable Fabric Act of 1953 contributed to the use of a new FR called Tetrakis(hydroxymethyl)phosphonium chloride (THPC). This compound belongs to the group of organophosphorus flame retardants (OPFRs) which are some of the most used FRs nowadays. The act regulated the manufacturing of clothes and furniture, and was a result of devastating fires in the past. The act lead to flammability standards and thereby a use of FRs to cope with them (CPSC 2016). The trends in fire protection and its legislation have for decades become stricter, leading to a greater use of FRs. This is especially evident in some parts of the world, including California. At the same time as Sweden and Europe began to ban certain FRs at the beginning of the 2000s, California established new laws requiring, for example, mattresses to handle an open flame for 30 minutes compared to the previous 3 minutes. Now, however, several states in the US (including California) have also followed the EU example and launched a phasing out of several FRs in the near future (Chemical Watch 2018). For example, Maine will ban all use of FRs in furniture from 2019 (Chemical Watch 2017). Nevertheless, a lot of FRs remain in Swedish and European products, even prohibited ones, since products imported from for example Asia may contain these substances. Another potential source of banned FRs is recycled plastic, as this is also not covered by the prohibition (Strakova et al. 2018). Some of the first more advanced FRs called the brominated FRs were also those that were first questioned and later banned. They are a large group of substances with different properties. A major setback occurred in the US in the 1970s when cattle were poisoned by polybrominated biphenyls (PBBs), which led to a ban of the PBBs . In total, there are about 80 brominated FRs, of which about 10 are totally or partially prohibited today. The laws for brominated FRs have generally become stricter but varies depending on the application and between countries. An example of this is that Sweden in 2007 introduced a national ban on all use of deca-BDE (a technical mixture of BDEs, mainly BDE209). But in 2008, the European Commission decided that all member states would ban deca-BDE except for use in the textile industry. This is being implemented in order for Swedish legislation to harmonize with the European one. However, this means that Swedish companies in the textile industry that have stopped using this substance will have a competitive disadvantage according to the Swedish Society for Nature Conservation (Naturskyddsföreningen 2008, Regeringskansliet 2008). Use and Exposure today FRs are present in houses built from the 1930s onwards (Hult & Lundblad 2007). They are used in the manufacture of different types of building materials, but also in furniture and electronics. In the 80's, the use of FRs began to accelerate seriously, and this was e.g. observed in breast 2 milk among Swedish women (Miljöbarometern 2017). This was a result of the plastic material being invented and started to be used on a larger scale. Plastic is good in many ways, but it is also very flammable and therefore there is a need of adding FRs (Blackburn 2009). Sometimes FRs are added to just reduce fire risk, but they may also have other features or accompany production where they have served as raw material, intermediates, stabilizers or adhesives. If the substance binds chemically to the material during the manufacturing process, it is released to the environment to a lesser extent during use (KEMI