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 2019a). However, a flame retardant can be released to the environment at various times; both during the manufacturing process, when the product is used but also when it is discarded and / or disassembled. Thus, it can be released throughout its life cycle, but the amount released at different times varies between substances (Marklund 2005). This is determined, among other things, by the substance's properties and how it is used. Some substances are volatile and emit easily into the air, while others are heavier and to a greater extent end up in soil and water. Whether these substances are then absorbed by organisms depends on many different factors; if they bind to particles, are broken down by sunlight or other external factors. Although they are rapidly decomposed in the environment, this does not necessarily mean that they are harmless as the degradation product can in some cases be very toxic. The Swedish Chemicals Agency (KemI) has a register of chemicals used by industry and the two FRs imported in the largest volumes in 2016 were Pentaerythritol and Tris(2-ethylhexyl) phosphate (TEHP), which are used in the paper industry, among other things (SPIN 2016). Fortunately, these substances have not been shown to have any major toxicity or to be carcinogenic (Pubchem 2019a, Pubchem 2019b). The world's most widely used FR is aluminum hydroxide which account for about 38% of the market but is principally harmless and is used in pharmaceuticals (Shon et al. 2020). Thereafter we have a big group of substances called organophosphates that stands for about 18%. Another big group is the brominated substances that make up about the same proportion of 17% of the world's production (IHS Markit 2017). In Sweden, the situation looks somewhat different, but it largely reflects the rest of the world with the globalized market of goods being exported and imported, which contain different chemicals. In the Swedish industry, the brominated substances account for less than 1% of the use since many substances are prohibited and use is regulated (KEMI 2010). However, large quantities of goods are imported from, among others, Asia, which means that the total amount of brominated FRs found in products (and the environment) becomes higher, but it is difficult to say an exact number since these goods are not declared in such a way. Another group of concern is the antimony oxides that are poorly studied. It is a high volume produced FRs that stands for about 9% of the global market. It can be assumed that these have harmful effects since antimony has similar properties to arsenic, which is environmentally hazardous (Encyclopaedia Britannica 2018, U.S. Department of Health and Human 2019, Naturvårdsverket 2019). Antimony is an unusual metalloid that has been used since ancient time as makeup, among other things. In the 21st century production has increased sharply (40%) and it is used together with halogenated substances where it has a synergistic effect and thus strengthens the efficiency of the FR (Turner & Filella 2017). In total, more than 2.25 million tons of FRs are produced each year, of which 50% are consumed in Asia, of which 26%in China. The western world also accounts for an almost equal share (about 45%), while the rest of the world's use in this context is small (IHS Markit 2017).
3 People and pets are often exposed to the highest concentrations when they are in an indoor environment or transported in vehicles. The substances can be both in the air but often accumulate in dust, which causes children and pets to be particularly exposed. You can also be exposed to these environmental toxins through food and drinking water (Schreder 2017). However, some parts of the population can be exposed to significantly higher levels in workplaces where these chemicals are handled (Gravel et al. 2019, Estill et al. 2020). Some of the substances are classified as harmful or hazardous and then there are provisions for how they should be handled and disposed of. One of the most common areas of use for flame retardants is in electronic equipment. In a Swedish study in the 1990s, significantly higher values of polybrominated diphenyl ethers (PBDE) were measured in the blood of factory workers at a company that disassemble electronics compared to other occupational groups (Sjödin et al. 1999). 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. The legislation also aims to improve the possibility of recycling materials in an environmentally friendly way. The directive has been implemented in several stages, and from 2019, almost all electronic equipment is covered (KEMI 2019b). Another legislation that is of great importance for these chemicals is the REACH Regulation, which came into force in 2007. This legislation aims to register all chemical products in the EU and to examine their properties. Legislation intends that substances that are found to have harmful effects on humans or the environment should be restricted or banned. In Sweden, the Swedish Chemicals Agency has the main responsibility for compliance with the legislation (KEMI 2019c). Many of the flame retardants are so-called persistent organic compounds (POPs), which are often halogenated. This means that they have high fat solubility, which leads to their accumulation in the fat tissue of organisms. Halogenation also makes them persistent and therefore they do not break down in nature which becomes problematic if they are harmful. These substances are regulated in the Stockholm Convention, whose purpose is to eliminate or limit the distribution of these substances. Almost all countries in the world have agreed to follow these guidelines, but the United States has not signed the agreement. The Stockholm Convention is now part of EU legislation (Smith 2015). More recently, environmental awareness has led to "green chemistry" becoming increasingly important in this area. Among other things, it has been discovered that natural oils can act as flame retardants when added to foam materials. This reduces the need for conventional flame retardants, which is beneficial for human health and the environment (Rowlands 2014).
Our study In a previous study, several Swedish rivers were examined, leading to a couple of watercourses with higher levels of FRs being discovered (Gustavsson et al. 2018). Therefore, one could assume that there were certain types of activities along these rivers that released FRs to the water. The purpose of this study was to investigate potential point sources of FRs and to identify 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, the study also included several legacy substances for comparison. The investigated potential point sources include several types of industries, but also airports, (Bruchajzer et al. 2015). Some other included, more indirect potential sources are snow dumps where pollution from traffic can accumulate, arable land where machines with hydraulic oil (often containing OPFRs) are used
4 and where the fields may be fertilized with sludge from waste water treatment plants (WWTPs )(Sundkvist et al. 2010). We also have storm water ponds where pollution from both traffic and industry may accumulate. Moreover, waste treatment facilities (WTFs) and WWTPs were included in the study. The risk of pollution coming into the environment is clearly due to the handling of these pollutants and chemicals, but also how the water is purified before it is released into a watercourse. Many industries are linked to a local sewage treatment plant and it is therefore these can become a point source for pollutants. In many cases, we have therefore chosen to test the main flow (the river), but also tried to find potential sources of emissions and to test the outflow from these. This has resulted in us sampling industries, airports, WTFs, snow dumps, WWTPs, agricultural lands, storm water ponds and rivers. By collecting water samples one can get a relatively good overall picture of the emission and can calculate the amount transported in the water flow (flux). When the water is collected with a so-called grab sampling it means that the result must be interpreted with great caution as it does not give a complete picture of the situation. Emissions of substances can vary over time and be affected by the seasons. For example, in the spring flood, both the water flow and the composition/concentration of substances may change. The substances vary greatly in their chemical properties, which means that they are distributed differently in the various elements (air, water and sediment). Some substances tend to accumulate in the bottom sediment while others move to the atmosphere. However, there is always a certain proportion of all substances in the water phase. The organisms living in the water are often susceptible to pollution. But even those living in the sediment can be sensitive, however, it has not been possible to take such samples in this study. Nor has it been possible to look for all FRs as there are hundreds of substances and new ones are being produced all the time. It has therefore been decided to focus on the substances that are produced in the largest quantities and/or are of the greatest importance for the environment.
Materials and methods My supervisor has been working at SLU for several years where he defended his doctoral thesis in 2017. He was one of the first in Sweden to investigate the presence of alternative FRs in the Swedish environment. To do this, he spent his first years developing analytical methods for these substances. It was important to be able to analyze both old and new FRs, for this purpose gas chromatography proved to work well (Gustavsson et al. 2017b). For some substances, however, liquid chromatography work better, but to save time and money, gas-chromatography is used for all substances. Before analyzing the substances, they need to be extracted and these methods were also developed and improved over the years (Gustavsson et al. 2017a).
Compounds In a previous literature study a total number of 66 new FRs were identified, of which 50 were concluded to be of high environmental relevance (Gustavsson et al. 2017c). Earlier, a screening study of Swedish rivers was conducted, searching for 61 different FRs, both legacy and new, of which 26 were found in the samples (Gustavsson et al. 2018b). Based on the literatute study and the findings from the previous screening, 63 substances were selected for this study, of which 11 are legacy compounds. Unfortunately, 4 of these compounds could not be measured because of analytical challenges which resulted in 59 compounds being analyzed (Table 1).
5 Table 1 FR target compounds sorted as halogenated, organophosphorus or legacy halogenated.
Substance Acronym CAS Halogenated FRs 2,4-Dibromophenol 24-DBP 615-58-7 2,6-Dibromophenol 26-DBP 608-33-3 2,4,6-Tribromophenol 246-TBP 118-79-6 2-Bromoallyl 2,4,6-tribromophenyl ether BATE na Bis(2-ethyl-1-hexyl)tetrabromo phthalate BEH-TEBP 26040-51-7 1,2-Bis(2,4,6-tribromophenoxy)ethane BTBPE 37853-59-1 1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane DBE-DBCH 3322-93-8 Hexachlorocyclopentadienyl dibromocyclooctane DBHCTD 51936-55-1 2,2-Dibromovinylbenzene DBS 31780-26-4 Dechlorane Plus, anti isomer aDDC-CO 13560-89-9 Dechlorane Plus, syn isomer sDDC-CO 13560-89-9 2-Ethylhexyl 2,3,4,5-tetrabromobenzoate EH-TBB 183658-27-7 Hexabromobenzene HBB 87-82-1 4,5,6,7-Tetrabromo-1,1,3-trimethyl-3-(2,3,4,5- OBTMPI 1084889-51-9 tetrabromophenyl)indane Pentabromobenzyl acrylate PBB-Acr 59447-55-1 Pentabromobenzylbromide PBBB 38521-51-6 Pentabromochlorocyclohexane PBCH 87-84-3 Pentabromoethylbenzene PBEB 85-22-3 Pentabromophenyl allyl ether PBPAE 3555-11-1 Pentabromotoluene PBT 87-83-2 Tetrabromobisphenol A TBBPA 79-94-7 1,2,5,6-Tetrabromocyclooctane TBCO 3194-57-8 1,2,3,4-Tetrabromo-5chloro-6-methylbenzene TBCT 39569-21-6 Allyl 2,4,6-tribromophenyl ether TBP-AE 221-913-2 2,3,5,6-Tetrabromo-p-xylene TBX 23488-38-2 Tetrachlorobisphenol-A TCBPA 27360-90-3 Organophosphorus FRs Bisphenol A bis(diphenyl phosphate) BADP 5945-33-5 2-Ethylhexyl diphenyl phosphate EHDPP 1241-94-7 Cresyl diphenyl phosphate CDP 26444-49-5 ortho-Tritolyl phosphate o-TMPP 1330-78-5 meta-Tritolyl phosphate m-TMPP 1330-78-5 para-Tritolyl phosphate p-TMPP 1330-78-5 Resorcinol bis(diphenyl phosphate) PBDPP 57583-54-7 Tri(2-chloropropyl) phosphate T2CPP 6145-73-9 Tri(3-chloropropyl) phosphate T3CPP 26248-87-3 Tri(2-butoxyethyl) phosphate TBOEP 78-51-3 Tris(4-tert-butylphenyl) phosphate TBPP 78-33-1
6 Tris(2-chloroethyl) phosphate TCEP 115-96-8 Tri(1-chloro-2-propyl) phosphate TCIPP 13674-84-5 Tris(1,3-dichloro-isopropyl) phosphate TDCIPP 13674-87-8 Tris(2-ethylhexyl) phosphate TEHP 78-42-2 Triisobutyl phosphate TiBP 126-71-6
Tri(2-isopropylphenyl) phosphate TiPPP 64532-95-2 Tri-n-butyl phosphate TNBP 126-73-8 Tripentyl phosphate TPeP 2528-38-3 Triphenyl phosphate TPHP 115-86-6 Tripropyl phosphate TPP 513-08-6 Tris(tribromoneopentyl) phosphate TTBNPP 19186-97-1 Legacy halogenated FRs 2,4,4’-Tribromophenyl ether BDE28 41318-75-6 2,2',4,4'-Tetrabromodiphenyl ether BDE47 5436-43-1 2,3′,4,4′-Tetrabromodiphenyl ether BDE66 189084-61-5 2,2',3,4,4'-Pentabromodiphenyl ether BDE85 82346-21-0 2,2',4,4',5-Pentabromodiphenyl ether BDE99 32534-81-9 2,2',4,4',6-Pentabromodiphenyl ether BDE100 189084-64-8 2,2',4,4',5,5'-Hexabromodiphenyl ether BDE153 68631-49-2 2,2′,4,4′,5,6′-Hexabromodiphenyl ether BDE154 207122-15-4 2,2',3,4,4',5',6-Heptabromodiphenyl ether BDE183 207122-16-5 Decabromodiphenyl ether BDE209 109945-70-2 3,3',4,4',5,5'-Hexabromobiphenyl BB-153 67774-32-7
Sampling sites and sampling There are pros and cons with sampling directly from the point source or downstream the source. When sampling directly from the source you get the amount that the source contributes with, and the substance are not being absorbed or broken down by processes in nature. The advantage of sampling downstream of the source is that you get the concentrations that occur in nature, but then it is not possible to say which sources (and how much) contributes to the effluent. In some places, it was for practical reasons not possible to sample directly from the source. This is true for some protected areas such as the airports. Sampling was done throughout Sweden at 29 different locations from Sundsvall in the north to Gothenburg in the south (Table 2 & Figure 1). Below follows a more detailed description of the various sampling locations. Agriculture One site was sampled where we received information that sewage sludge was stored (referred to as the Shooting range), which is then used for fertilization of arable land. At this site there are several human activities such as golf and shooting that also can give rise to contamination of the environment. The site was classified as farmland because it was the main area of use. Also, a small family farm with ongoing agricultural activity was sampled (Sörtuna gård). In this area there are likely no major emission points of FRs.
7 Airports & Stormwater Several commercial airports were sampled but also one military airport. At Sweden's largest airport (Arlanda), we chose to collect water in Halmsjöbäcken, which is the same place as they themselves do their environmental monitoring. The military airport was located in Uppsala (Ärna), which previously was a target for environmental investigations in connection with the finding that perfluorinated alkylated substances (PFAS) leaked into the groundwater. To this airport, it was particularly difficult to get access to, but because of the already ongoing investigations, we could gain access to water samples collected by an external company. One of southern Sweden's largest airports is located in Landvetter (outside the big city of Gothenburg) and samples were taken at two locations downstream, one of which is a lake (Issjön) and one is a river (Issjöbäcken). Another airport of interest was Skavta Airport because it has an outflow in Nyköpingsån where earlier studies (Gustavsson et al. 2018b) measured high levels of FRs. Samples were taken directly at the outflow, but also upstream of the airport in Nyköpingsån. The northernmost airport sampled was Sundsvall-Timrå airport. This one is connected to the Indalsälven river and thesampling points are located downstream of several potential point sources, of which a storm water pond (Vivsta) which was also sampled. To this stormwater pond, water is drained from an industrial area where there is a risk of emissions. This stormwater pond has previously been failed for its inadequate purification and therefore had to be remedied. At the time of sampling the pond was in the process of remediation and the water was therefore directed past the pond and directly into the river without being cleaned and this water was collected. Different types of stormwater pounds around Sweden were investigated to see if there is any FRs accumulation in these and if it ends up in the watercourses. Five dams were sampled (one of which serves as a snow dump in the winter) from Sundsvall in the north to Gothenburg in the south. Industries We also wanted to sample a wide range of industries. Finding suiTable candidates was a challenge, as most of them are affiliated with local treatment plants and private companies do not want to get any negative publicity when the results are presented. This resulted in one paper industry (with their own treatment plant) and one car industry (connected to the municipal sewage treatment plant) being sampled. Worth mentioning is that we were not allowed access to the car company and therefore these water samples were collected by the company itself. WTF (waste treatment facilities) Another place where various pollutants may accumulate with the risk of being spread to the environment are different types of waste facilities. We sampled four, of which one was specialized in hazardous waste. At three of these, leachate was sampled inside the area, but at the plant that handles hazardous waste, outgoing cooling water (Fortum) was sampled. At one of the facilities (Högbytorp), a recipient was also sampled after the leachate had flowed through arable land. WWTP (wastewater treatment plants) Another point source that is believed to accumulate large amounts of environmental pollutants is municipal sewage treatment plants which often take care of many types of wastewater (including water from industries). In total, five treatment plants were sampled, of which one (Ryaverket) took care of water from the car industry that we also sampled.
8 Table 2 Sampling sites. Cate Coordi Site City Description gory nates N65201 Stream draining agricultural land where biosludge have been applied to fields. Biosludge storage Shooting Agricult Nykö 23, approx. 1 km from stream but no obvious connectivity between sludge storage and the sampled range ure ping E61169 stream. 9 N65327 Sörtuna Agricult Nykö 21, Ditch draining agricultural land where no biosludge have been applied to fields. gård ure ping E64217 4 N66138 Halmsjöbä Stock 78, Airport Stream downstream Arlanda airport. cken holm E66249 6 N63907 Göte 16, Issjön Airport Lake downstream Landvetter airport. borg E33733 5 N63890 Issjöbäcke Göte 55, Airport Stream downstream Landvetter airport. n borg E33786 1 N65182 Nykö 84, Skavsta Airport Outflow from Skavsta airport before water is reaching wetland. ping E61181 9 N69340 ST airport, Sund 27, River Indalsälven. Sampled close to the outlet from Sundsvall-Timrå airport. Also downstream of e.g. Airport east svall E62606 the outlet from Vivsta stormwater pond. 8 N69342 ST airport, Sund 70, River Indalsälven. Sampled close to outlet from Sundsvall-Timrå airport. Also downstream of e.g. the Airport west svall E62510 outlet from Vivsta stormwater pond. 1 N66428 Airport Upps 12, Ärna (militar Outflow from Ärna military airport. ala E64481 y) 9 N64011 Car Göte 89, Volvo industr The effluent from Volvo WWTP. Further treated in the municipal WWTP (Ryaverket). borg E31676 y 0 N67253 Pulp Skutskär Upps 55, industr River water (River Dalälven) intake for use during pulp production. IN ala E63111 y 2 N67265 Pulp Skutskär Upps 82, industr Outflow from the pulp industry WWTP. OUT ala E63136 y 9 N65226 Re- Nyköpings Nykö 86, Outlet from Lake Långhalsen. Located in an area where biosludge are applied to fields. Upstream of sample ån ping E61111 outlet from Skavsta airport. d river 4 N66422 Snow Snow Upps 21, Meltwater from city snow dump site. dump dump ala E64878 8 N63932 Järnbrotts Stormw Göte 36, Outflow from sedimentation pond. Mixed catchment with ~60 000 vehicles day-1, larger roads, dammen ater borg E31693 residential and industrial areas. 0 N65704 Skebäcksd Stormw Öreb 17, Pond draining mixed urban catchment with some industries. ammen ater ro E51466 6 N65785 Essingeled Stormw Stock Well mainly draining a heavily trafficked road (Essingeleden) with a yearly average of 154 000 vehicles 77, en ater holm per day. E67128
9 1 N66366 Uppsala Stormw Upps 51, stormwate Sedimentation pond. Catchment with larger roads, retail and car workshops. ater ala E65303 r pond 4 N69329 Stormw Sund 66, Vivsta Catchment draining industrial area and forest. Sample taken before sedimentation pond. ater svall E61859 4 N66471 Hovgårde Upps 32, Outflow from WTF's WWTP. Household waste, biosludge storage, landfill for non-hazardous waste, WTF n ala E65506 sorting of e.g. industrial waste and construction material. 8 N63973 Göte 78, Fläskebo WTF Landfill for mainly surface materials (Swedish: schaktmassor). Outlet from sedimentation pond. borg E33042 9 N65529 Öreb 30, Downstream Fortum waste solutions WTF with e.g. high-temperature incineration, landfill and Fortum WTF ro E51557 treatment of hazardous waste. 0 N66041 Stock 54, Landfill leachate before reaching sedimentation pond. Permission for landfill of both hazardous and Högbytorp WTF holm E64782 non-hazardous waste. 4 N66027 Högbytorp Stock 35, WTF Downstream Högbytorp WTF. recipient holm E64900 7 N66369 Kungsängs Upps 23, WWTP Outflow from Uppsala's main WWTP, treating around 2200 m3/h. verket ala E64887 1 N66505 Upps 89, Storvreta WWTP Outflow from Storvreta WWTP with capacity of treating 220 m3/h. ala E65063 5 N63992 Göte 61, Ryaverket WWTP Outflow from Göteborg's main WWTP, treating around 14 000 m3/h. borg E31483 0 N65705 Skebäcksv Öreb 96, WWTP Outflow from Örebro's main WWTP, treating around 2000 m3/h. erket ro E51482 2 N65788 Stock 32, Henrikdal WWTP Outflow from Stockholm's main WWTP, treating around 11 000 m3/h. holm E67694 9 WTF: waste treatment facility: WWTP: waste water treatment plant
10
Figure 1. A map of Sweden showing the sampling sites. The sampling was performed during the winter of 2018 (January-April) and the samples were analyzed at the POPs laboratory in the Department of Aquatic Sciences and Assessment (IVM) at the Swedish University of Agricultural Sciences (SLU) in Uppsala.
The sample containers were cleaned using a comprehensive procedure in the lab beforebeing filled in during sampling. The containers were repeatedly rinsed with ethanol, acetone and water of increasing purity. The water filters were also cleaned (burned in an oven) and stored so that they would not be exposed to pollutions. Before sampling begun, water from the source was pumped through the equipment for about 5 minutes and the vessels were rinsed 3 times with the sample water before filling.
Sampling was conducted by pumping water through glass fiber filters (Whatman™ Glass Microfiber Filters GF/F™, 297 mm diameter, 0.7 μm pore size) until it became saturated and began to leak which was determined by the amount of particles in the water source. The sampled water volume varied between 2 and 200 liters. Sometimes the water was so pure that the filter never became saturated, but then pumping was stopped at 200 liters of water. At each sampling site two filters were used, and a stainless steel can of about 12 liters was filled with the filtrate. The filters were used to analyze the amount of flame retardant bound to particles and what proportion is in the dissolved phase. At two sampling sites (Volvo and Ärna), the only possibility of getting water samples was that otherscollected them for us. At two of the WWTPs (Kungsängsverket and Henriksdal), there was the opportunity to take flow-integrated water samples (during approx. 7 days), which was carried out by the employees at the plants. These four samples were filtered in the lab along with water collected at Högbytorp's recipient.
11 In total, samples were taken at 29 sites consisting of 42 filters and 42 water samples. This includes 12 duplicates, 10 field blanks and 2 laboratory blanks.
In addition, two polypropylene bottles were filled during sampling, the water from one of which was used to analyze SPM (solid particulate matter) and TOC (total organic carbon) while the other water bottle was for another research project. Water temperature and pH were also measured in the field (when possible). Field water blanks were also taken, which was done by opening steel cans filled with Millipore water for a short time at the sampling site and then being shipped back to the lab. In addition, filter blanks were taken and these were exposed to the air at the sampling site and then treated in the same way as the usual samples. In addition, lab blanks were taken, both water and filters. These were taken by pumping 10 liters of pure water (Millipore water) through the same equipment as used in the field. All the water samples were stored in a cold room where the temperature was about +8 degC while the filters were stored in a freezing room where the temperature was about -18 degC.
Analysis The water samples were extracted with a so-called solid phase extraction (SPE) which in this case means that the water was pumped through an Oasis® HLB cartridge (6 g, Waters, Massachusetts, USA) selected for the purpose of capturing a wide range of substances. The water stored in the cold room was fortified with 100 µL isotopically labeled internal standard (IS) mixture (c = 200-1000 µg µL-1) and mixed by shaking. Then it was allowed to stand overnight in the cold room (about 15 hours). Before the cartridge could be used, they were pre- conditioned with 20 ml of methanol and 20 ml of MilliPore water. When the entire sample volume had passed through, the tubes were dried by centrifugation (1000 rpm for 10 min). To elute the cartridge, 50 ml of dichloromethane (DCM) was poured into the stainless steel can and used to rinse the inside of the container. This was done 3 times so that all the residue of the substance would follow. Also, a small amount of DCM (about 10 ml) was used to rinse the inner walls of the cartridge. This gave a total volume of 160 ml for the elution.
Subsequently, any remaining water in the cartridge was removed as a result of the process using a Horizon DryDisk® membrane. Then the samples were concentrated with a TurboVap® II evaporator to a volume of about 1 ml. Then the samples were cleaned to remove some unwanted contaminants that could affect the instrumental analysis. The cleaning was performed by passing the sample through a test tube prepared with ~ 1 g sodium sulphate (removing water) and aluminum (removing impurities). Finally, a so-called solvent exchange was performed in an N-Evap® solvent evaporator where the solvent was changed from DCM to Toluene with a final volume of about 0.5 ml. For some samples, the cleaning procedure needed to be repeated, this was the case for the following samples; water samples from Skavsta, Kungsängsverket, Shooting range, Högbytorp, Vivsta, Volvo, Issjön and filter samples from Skavsta and Vivsta. This was done because there were unclear results in the gas chromatography (GC) analysis which was probably due to the matrix interfering. Before the analysis could begin, the samples were fortified with 10 μL of a recovery standard (RS, c = 1000 pg μL-1).
The filters followed another procedure called Soxhlet Dean-Stark extraction. This means that the filters are treated with a solvent, in this case toluene which has been shown to be good for dissolving different types of flame retardants (Altweiq et al. 2003). As for the water samples, the samples were spiked before extraction with 100 μL of IS mixture (c = 200-1000 pg μL-1). The two filters from each sampling site were extracted together and run for one day (about 20 hours). Subsequently, the filter samples were treated in the same way as the water samples.
12 Finally, the substances were analyzed using gas chromatography (GC) coupled to a tandem mass spectrometer. The method is described in detail in a previously published article (Gustavsson et al. 2019).
Quality assurance/Quality control (QA/QC) When detecting target compound and internal standard, a signal-to-noise (S/N) ratio ≥3 with a matching ion ratio (ion ratio within ± 20) was required for a posivitive detection. In addition, the retention time should be correct and the error margin was ± 0.1 min. To correct for losses, the isotope dilution quantification method was used. Recoveries of internal standards (IS) varied (Tables A1 and A2 in Appendix), probably due to a variable matrix that was sometimes complex. One of the criteria for using the data was 5% recovery of the IS. Due to the varying and sometimes low recoveries, all data for concentrations and fluxes should be interpreted with caution.
The MDL (method detection limit) was calculated for each substance using field blanks and the following formula. 푀퐷퐿 = 푎푣푒푟푎푔푒 푐표푛푐푒푛푡푟푎푡푖표푛 표푓 푏푙푎푛푘푠 + 3 ∗ 푠푡푎푛푑푎푟푑 푑푒푣푖푎푡푖표푛 표푓 푏푙푎푛푘푠
The MQL (method quantification limit) was determined by calculations based on MDL. If it was not possible to measure any concentration in the blank, then the lowest peak in the calibration curve was used as MDL. 푀퐷퐿 푀푄퐿 = ∗ 10 3
The average concentration (n = 5) for field blanks and MDL was calculated for water and filter samples respectively. When looking at all samples together (both water and filter) the field blank concentration ranged from not detected to 300 ng and the MDL ranged from 0.00058 to 39 ng / L (Table 3).
Table 3 Blank concentrations and method detection limits (MDLs).a Adopted from (Gustavsson et al. 2018a). Water Filter
Average blank MDL Average blank MDL Compound (ng absolute, n = 5) (ng L-1) (ng absolute, n = 5) (ng L-1)
24-DBP ND 3.8 ND 0.88
26-DBP ND 1.9 ND 0.44
aDDC-CO ND 0.010 ND 0.0022
ATE ND 0.029 ND 0.0066 HFR BATE ND 0.029 ND 0.0066
BB-153 ND 0.029 4.7 0.26
BEH-TEBP ND 1.9 ND 0.44
BTBPE ND 0.24 ND 0.055
13 DBE-DBCH ND 0.010 ND 0.0022
DBHCTD ND 0.24 ND 0.055
DBS ND 0.24 ND 0.055
EHTBB ND 0.24 ND 0.055
HBB ND 0.010 ND 0.0022
OBTMPI ND 7.6 ND 1.8
PBB-Acr ND 0.24 0.13 0.020
PBBBr ND 1.9 ND 0.44
PBEB ND 0.029 ND 0.0066
PBPAE ND 0.24 ND 0.055
PBT ND 0.010 0.048 0.0048
sDDC-CO ND 0.048 ND 0.011
TBBPA ND 19 ND 4.4
TBCO ND 0.24 ND 0.055
TBCT ND 0.029 ND 0.0066
TBP 300 140 6.2 0.95
TBX ND 0.010 ND 0.0022
TCBPA ND 19 0.72 0.050
BADP 17 7.3 0.23 0.022
CDP ND 1.9 ND 0.44
EHDPP 2.6 1.6 0.013 0.0020
mTMPP ND 0.010 ND 0.0022
oTMPP ND 0.010 0.0059 0.00058
pTMPP ND 0.24 300 39
RDP ND 7.6 ND 1.8
TBOEP ND 0.24 ND 0.055 OPFR TBPP ND 0.010 ND 0.0022 TCEP 1.3 0.86 4.1 0.36
TCIPP 120 53 46 3.2
TDCIPP 1.2 0.40 1.7 0.16
TEHP ND 0.010 ND 0.0022
TIBP ND 0.010 ND 0.0022
TiPPP 9.7 2.9 0.89 0.086
TNBP 75 28 9.2 0.85
14 TPeP ND 19 ND 4.4
TPHP 18 6.9 11 0.55
TPP ND 0.029 0.37 0.057
TTBNPP ND 0.029 ND 0.0066
BDE28 ND 0.029 4.4 0.24
BDE47 ND 0.048 0.041 0.0063
BDE66 ND 0.048 0.11 0.012
BDE85 ND 0.24 0.075 0.012
BDE99 ND 0.24 0.11 0.017 PBDE BDE100 ND 0.048 0.041 0.0063
BDE153 ND 0.24 ND 0.055
BDE154 ND 0.24 0.068 0.011
BDE183 ND 1.9 ND 0.44
BDE209 37 12 ND 0.88 a ND = not detected
Calculation of river fluxes To calculate fluxes of the individual substances, either the measured water flow for the specific day was used or the water flow was estimated with models. In many cases, the value for the specific day could be provided by staff working at the facility. If this could not be obtained a monthly or annual average value was used. In some places neither measurement data nor models could be used and therefore no fluxes were calculated. Keep in mind that both concentration data and calculated fluxes contain considerable uncertainty.
15 Results Detection frequency At all sampling places at least one FR was found, and the highest number was measured at Högbytorp waste facility, where 23 were found (Figure 2). Then comes Skavsta Airport with 17 substances, followed by Ärna Airport, Fortum WTF and Ryaverker WWTP with 16 substances each. When comparing different types of plants / sites, the largest number of substances was obtained at the WTFs, 15 (± 5). In the lab blank, two substances were obtained but at low concentrations (<1.1 ng / L).
Number of detected FRs 0 5 10 15 20 25 Shooting range Sörtuna Halmsjöbäcken Issjöbäcken Issjön Skavsta Skavsta ST airport, east ST airport, west Ärna Skutskär OUT Skutskär OUT Volvo Volvo Nyköpingsån Skutskär IN Essingeleden Järnbrottsdammen Järnbrottsdammen Skebäcksdammen Snow dump Uppsala stormwater pond Vivsta Fläskebo Fortum Hovgården Hovgården Högbytorp Högbytorp recipient Henriksdal (flow-int) Henriksdal (grab) Kungsängsverket Kungsängsverket Ryaverket Skebäcksverket Storvreta Lab blank
Figure 2. Number of detected FRs (>MDL) at each site (filter + water). Orange bar = agricultural sites, light blue = airport sites, green = industrial sites, yellow = river sites, grey = stormwater sites, dark blue = waste treatment facility (WTF) sites, black = wastewater treatment plant (WWTP) sites, and purple = the laboratory blank sample. The Asterix marks sampling locations where replicates have been taken and the value is therefore an average.
16 The OPFRS are dominating when looking at the most frequent detected FRs (>MDL) in this study and of the five most detected FRs, four were OPFRs. These five were detected as following; TDCIPP (78% of all samples), BDE66 (68%), TEHP (57%), TCIPP (57%), and TBOEP (57%) (Figure 3).
Detection frequency (%)
TBBPA BB-153 ATE PBB-Acr TBX sDDC-CO 246TBP PBT TCBPA BDE183 BDE85 BDE153 BDE47 BDE154 BDE100 BDE99 BDE66 TBPP pTMPP RDP oTMPP TiPPP mTMPP TTBNPP TPHP TNBP BADP TIBP EHDPP TCEP TBOEP TCIPP TEHP TDCIPP 0 10 20 30 40 50 60 70 80 90
Figure 3. Detection frequency (%) of all detected FRs (>MDL). Blue = halogenated FRs (HFRs), green = polybrominated diphenyl ethers (PBDEs) and yellow bar = organophosphorus FRs (OPFRs). Total concentration The total concentration, the sum of all flame retardants ranged from 0 ( resulting in a TOC of >800 mg/L. Therefore, the value of FR's concentration at this location should be 17 interpreted with extra caution. In the laboratory blank a value of 1.7 ng/L was measured which is lower than in most sampling sites. The organophosphates usually contributed most to the concentration (76% of the total). 160000 A ) 1 140000 - 120000 100000 80000 60000 40000 Total bulk concentration (ng L (ng concentration bulk Total 20000 0 Ärna Issjön Volvo Vivsta Fortum Sörtuna Skavsta Fläskebo Storvreta Lab blankLab Ryaverket Högbytorp Hovgården Issjöbäcken Skutskär IN Snow dump Essingeleden Nyköpingsån Skutskär OUT Shootingrange ST ST airport, east Halmsjöbäcken Skebäcksverket Kungsängsverket Henriksdal (grab) Skebäcksdammen ST ST flygplats,west Järnbrottsdammen Högbytorp recipient Henriksdal (flow-int) Uppsala stormwater pond B 12000 ) 1 - 10000 8000 6000 4000 2000 Total bulk concentration (ng L (ng concentration bulk Total 0 Ärna Issjön Volvo Vivsta Fortum Sörtuna Fläskebo Storvreta Lab blankLab Ryaverket Högbytorp Hovgården Issjöbäcken Skutskär IN Snow dump Essingeleden Nyköpingsån Skutskär OUT Shooting range ST ST airport, east Halmsjöbäcken Skebäcksverket Kungsängsverket Henriksdal (grab) Skebäcksdammen ST ST flygplats,west Järnbrottsdammen Högbytorp recipient Henriksdal (flow-int) Uppsala stormwater pond Figure 4. Total bulk FR concentrations (ng L-1) for each of the sampled sites. Error bars represent the standard deviation (n = 2). A) Including Skavsta airport. B) Excluding Skavsta airport (for visibility). 18 Fluxes Using the concentration values and the flow data, fluxes could be calculated. These ranged from 0 to 1.8 kg / day (Figure 5). Keep in mind that these values should also be interpreted with caution as the data that underlies them often comes with great uncertainty. Five sites had remarkably higher fluxes than the others. Three of these sites were WWTPs (0.18-1.8 kg / day), which is not surprising as they handle large amounts of contaminated water. The fourth place was Skavsta Airport (0.21 ± 0.27 kg / day) which differed from the other airports with a relatively high value. 2 000 A 1 800 ) 1 - 1 600 1 400 1 200 1 000 800 600 Total FR flux (g (g flux day FR Total 400 200 0 B 16 ) 1 14 - 12 10 8 6 4 Total FR flux (g (g flux day FR Total 2 0 Ärna Volvo Fortum Fläskebo Storvreta Högbytorp Hovgården Issjöbäcken SkutskärIN Essingeleden Nyköpingsån SkutskärOUT ST airport, east STairport, Halmsjöbäcken ST airport, west STairport, Kungsängsverket Skebäcksdammen Järnbrottsdammen Högbytorp recipient Högbytorp Uppsala stormwater pond Uppsalastormwater Figure 5. Total bulk FR flux (g day-1) for each site (for sites with available water mass flow data). A) Including all sites. B) Excluding the five highest fluxes (for better visibility). 19 Composition profile Of the 59 substances we were looking for, 34 were found in the samples. Of these, there were 17 OPFRs, 8 alternative HFRs and 9 were legacy HFRs. In most places, the organophosphates dominated, while the halogenated substances accounted for a smaller proportion. The legacy compounds usually accounted for only a fraction of the composition (Figure 6). 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% Shooting range ST airport, west Issjöbäcken Skavsta Ärna Volvo Skutskär OUT Nyköpingsån Essingeleden Järnbrottsdammen Skebäcksdammen Vivsta Fläskebo Hovgården Högbytorp Henriksdal (grab) Kungsängsverket Skebäcksverket ∑Alternative HFRs ∑OPFRs ∑Legacy HFRs Figure 6. Compositional profile (including compounds detected >MDL) of ∑alternative HFRs, ∑OPFRs and ∑legacy HFRs (i.e. PBDEs and BB-153) for each site. Composition profile is relatively similar between the different sites and it is not possible to say that a certain type of place emits a certain type of substances. However, it can be said that the sites that emit higher concentration of substances and usually have higher fluxes often have a higher complexity in the profile with both new and old substances (Figure 7). For example, Högbytorp has the highest number of substances (23), also one of the highest total concentrations and a relatively high flux. 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% Shooting range ST airport, west Issjöbäcken Skavsta Ärna Volvo Skutskär OUT Nyköpingsån Essingeleden Järnbrottsdammen Skebäcksdammen Vivsta Fläskebo Hovgården Högbytorp Henriksdal (grab) Kungsängsverket Skebäcksverket 246TBP ATE BB-153 PBB-Acr PBT sDDC-CO TBBPA TBX TCBPA TDCIPP TEHP TCIPP TBOEP TCEP EHDPP TIBP TNBP BADP TPHP TTBNPP mTMPP TiPPP oTMPP RDP TBPP pTMPP BDE47 BDE66 BDE85 BDE99 BDE100 BDE153 BDE154 BDE183 Figure 7. Compositional profile (including compounds detected (>MDL) of all detected FRs for each site. Toxicity Two-thirds of the substances found in the current study have been classified as environmentally hazardous as they are toxic, persistent and accumulate in the food chain (ECHA 2020, PubChem 2020a). Of these ecotoxic substances, almost half are already banned because of these properties (Table 4). Table 4. Substances found in this study have been classified into four different categories based on their environmental hazards (and colored for visibility). The color coding shows the degree of toxicity; red (toxic), orange (moderate), yellow (unclear) and green (harmless). Environmentally Compound Acronym Reference hazardous Halogenated FRs 2,4,6-Tribromophenol 246-TBP YES PubChem & ECHA Dechlorane Plus, syn isomer sDDC-CO YES PubChem & ECHA Pentabromobenzyl acrylate PBB-Acr Possible PubChem Pentabromotoluene PBT No (irritant) PubChem & ECHA Tetrabromobisphenol A TBBPA YES PubChem & ECHA Allyl 2,4,6-tribromophenyl ether TBP-AE (ATE) Possible (Asnake et al. 2015) 2,3,5,6-Tetrabromo-p-xylene TBX No (irritant) PubChem & ECHA Tetrachlorobisphenol-A TCBPA Possible (Tian et al. 2017) Organophosphorus FRs Bisphenol A bis(diphenyl phosphate) BADP Possible Waaijers et al. 2-Ethylhexyl diphenyl phosphate EHDPP YES Pubchem ortho-Tritolyl phosphate o-TMPP YES PubChem & ECHA meta-Tritolyl phosphate m-TMPP YES PubChem & ECHA para-Tritolyl phosphate p-TMPP YES PubChem & ECHA Resorcinol bis(diphenyl phosphate) PBDPP (RDP) YES Pubchem & Echa Tri(2-butoxyethyl) phosphate TBOEP moderate PubChem Tris(4-tert-butylphenyl) phosphate TBPP Not shown (misssing data) - Tris(2-chloroethyl) phosphate TCEP YES PubChem & ECHA Tri(1-chloro-2-propyl) phosphate TCIPP No (irritant) PubChem & ECHA Tris(1,3-dichloro-isopropyl) phosphate TDCIPP YES PubChem & ECHA Tris(2-ethylhexyl) phosphate TEHP No (irritant) PubChem & ECHA Triisobutyl phosphate TiBP Possible PubChem Tri(2-isopropylphenyl) phosphate TiPPP Possible PubChem Tri-n-butyl phosphate TNBP YES PubChem & ECHA Triphenyl phosphate TPHP YES PubChem & ECHA Tris(tribromoneopentyl) phosphate TTBNPP Not shown (missing data) - Legacy halogenated FRs 2,2',4,4'-Tetrabromodiphenyl ether BDE47 YES (Parry et al. 2018) 2,3′,4,4′-Tetrabromodiphenyl ether BDE66 YES (Parry et al. 2018) 2,2',3,4,4'-Pentabromodiphenyl ether BDE85 YES (Parry et al. 2018) 2,2',4,4',5-Pentabromodiphenyl ether BDE99 YES (Parry et al. 2018) 2,2',4,4',6-Pentabromodiphenyl ether BDE100 YES (Parry et al. 2018) 2,2',4,4',5,5'-Hexabromodiphenyl ether BDE153 YES (Parry et al. 2018) 2,2′,4,4′,5,6′-Hexabromodiphenyl ether BDE154 YES (Parry et al. 2018) 2,2',3,4,4',5',6-Heptabromodiphenyl ether BDE183 YES (Parry et al. 2018) 3,3',4,4',5,5'-Hexabromobiphenyl BB-153 YES (Parry et al. 2018) 22 Some of the sites with the lowest concentration of flame retardants (Shooting range and Sörtuna) also turn out to have substances that are currently considered harmless (ECHA 2020, PubChem 2020a). In most places, there is a high proportion of ecotoxic substances, some of which are prohibited (Figure 9). When risk assessing and classifying a substance, it is based on the properties of the substance. The toxic properties of the substance are evaluated (LD50, EC50 or equivalent), persistence (how quickly it breaks down in the environment) and whether it is bioaccumulated (stored in the tissue of organisms with increased concentration in the food chain). The data is based partly on chemical and physical experiments but also on animal experiments. Most substances are tested primarily on aquatic organisms but can also be tested on mammals if deemed necessary. If a substance is classified as PBT / vPvB substance (Persistent, bioaccumulative and toxic / very persistent and highly bioaccumulative) then they should be phased out according to European law (KEMI 2016). 23 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% Shooting range Sörtuna Halmsjöbäcken ST airport, west ST airport, east Issjöbäcken Issjön Skavsta Skavsta Ärna Volvo Volvo Skutskär OUT Skutskär OUT Skutskär IN Nyköpingsån Essingeleden Snow dump Järnbrottsdammen Järnbrottsdammen Skebäcksdammen Uppsala stormwater pond Vivsta Fläskebo Fortum Hovgården Hovgården Högbytorp Högbytorp recipient Henriksdal (flow-int) Henriksdal (grab) Kungsängsverket Kungsängsverket Ryaverket Skebäcksverket Storvreta Lab blank 246TBP ATE BB-153 PBB-Acr PBT sDDC-CO TBBPA TBX TCBPA TDCIPP TEHP TCIPP TBOEP TCEP EHDPP TIBP TNBP BADP TPHP TTBNPP mTMPP TiPPP oTMPP RDP TBPP pTMPP BDE47 BDE66 BDE85 BDE99 BDE100 BDE153 BDE154 BDE183 Figure 9. Compositional profile (including compounds detected (>MDL) of all detected FRs for each site. The color coding shows the degree of toxicity; red (toxic), orange (moderate), yellow (unclear) and green (harmless). Discussion/conclusion In total, 34 out of 59 substances were found in this study. There was a wide range of FRs; halogenated, organophosphates and legacy substances. One interesting thing is that 9 of these were PBDEs that are banned in the EU. However, these were in relatively low concentrations, while mainly organophosphates accounted for the largest quantity. It is not surprising that you find prohibited substances because they break down slowly and still occur in old or imported products. The places where most substances and highest concentrations were found were at the WWTPs and WTFs. This is not surprising as most of our pollutants should end up here, but it is alarming that the water we have sampled (often) is considered purified and that many flame retardants are still present in the water released into nature. The high values measured at Skavsta Airport can either be the result of the analysis being affected by the high TOC values that probably came from an emission of glycol. Alternatively, the presence of glycol caused environmental pollutants such as flame retardants to suspend to a greater extent in the water. A contributing factor to the high levels of flame retardants at Högbytorp's waste facility may have been that these samples were taken before undergoing water treatment. Although many of the FRs is not affected by treatment and the result may have been similar. In another study, the highest measured PBDE concentrations was 133 000 ng/L (leachate from a landfill), which is significantly higher than in our study (5.3 ng / L) (Stubbings & Harrad 2014). For example, for BDE-209, the toxic concentration is considered to be about 5 000 ng/L (EC50) which is a thousand times higher than our highest concentration (sum of all PBDEs) (Cristale et al. 2013). In the case of OPFRs and HFRs, the concentration should be in the order of 1 000 000 ng/L to cause damage to living organisms (Cristale et al. 2013, PubChem 2020b) In our study, the highest measured concentration is 150 000 ng/L, but this value has some uncertainty factors and the highest value we can confirm with relatively high certainty was 500 ng/L (A15 in appendix). That being said, we did not find any concentration that is close to those known to cause environmental damage. However, it cannot be ruled out that the concentrations we have found in the environment are completely harmless because the mechanism of toxicity is complex. In addition, many of these new substances are poorly studied and the result of a cocktail of these is not known. Thanks I want to thank SLU who made it possible for me to carry out my master's thesis. However, this would not have been possible without the support from the Swedish Environmental Protection Agency. I would also like to thank all the companies and municipalities that have allowed us to take samples of their facilities. I would especially like to thank my supervisor Jakob Gustavsson for his expertise and good cooperation. We have traveled through Sweden together and often worked side by side in the lab to be able to complete the results on time. I would also like to thank both Jakob, my opponent Lutz Ahrens, my friends and family who have contributed with feedback. I want to thank my examiner Lage Cerenius but also Henrik Viberg who was my examiner/coordinater during the first part of the project. It has been an interesting and rewarding project to be a part of, and it will be exciting to follow the development. 25 References Altweiq A, Wolf M, Eldik R. 2003. 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Toxicological Profile for Antimony. 282. 28 Appendix Please note that all data in the appendix can also be found in the report to the Swedish Environmental Protection Agency; Screening of replacement substances for the brominated flame retardants PBDE, HBCDD and TBBPA (Gustavsson et al. 2018a). TABLE A1 RECOVERY (%) OF INTERNAL STANDARDS (IS) IN WATER SAMPLES. Sample M-BDE47 M-BDE99 M-BDE100 M-BDE153 M-BDE154 M-BDE183 M-BDE209 M-TNBP M-TPHP M-HBB M-EHTBB M-aDDC-CO Essingeleden 95 63 57 27 24 15 2 207 109 112 50 24 Field blank 197 93 52 1 0 1 6 153 167 124 0 31 Field blank 91 52 35 0 0 1 7 79 71 67 0 14 Field blank 169 89 60 2 6 0 4 248 231 94 4 22 Field blank 162 22 51 1 0 0 6 198 177 91 0 23 Field blank 93 59 74 23 35 17 0 59 60 102 79 22 Fläskebo 106 78 66 21 22 0 3 219 69 157 69 17 Fortum 58 60 106 40 44 34 1 49 52 68 71 41 Halmsjöbäcken 69 73 85 59 63 48 1 40 18 58 90 48 Henriksdal 78 63 26 10 12 1 4 156 143 116 14 11 (flow-int) Henriksdal (grab) 134 26 87 7 10 0 12 396 231 78 0 11 Hovgården 61 47 35 17 18 14 2 98 56 69 48 12 Hovgården 71 56 59 36 37 33 5 47 59 70 44 20 Högbytorp 54 23 22 4 8 5 0 9 15 75 18 4 Högbytorp recipient 157 6 0 4 8 0 20 299 293 34 0 13 Issjöbäcken 99 36 27 2 10 0 2 126 143 68 3 10 Issjön 0 1 26 0 0 0 0 9 0 0 0 0 Järnbrottsdammen 79 61 57 35 41 28 2 60 46 74 40 33 Järnbrottsdammen 128 57 32 0 0 0 0 340 196 84 2 21 Kungsängsverket 30 9 9 4 5 3 0 20 4 20 7 4 Kungsängsverket 117 50 54 10 19 18 0 17 5 127 41 24 Lab blank 153 92 345 4 0 1 7 342 275 137 5 9 Nyköpingsån 82 80 91 50 58 37 2 35 48 80 83 36 Ryaverket 67 58 59 13 39 25 4 56 70 81 44 32 Shooting range 0 0 2 0 0 0 0 5 0 0 0 0 Skavsta 83 25 33 6 10 8 0 42 40 92 22 11 Skavsta 84 67 62 37 50 32 0 17 8 90 53 39 Skebäcksverket 80 20 58 0 1 2 10 182 139 52 1 10 Skutskär IN 121 32 48 2 1 0 3 56 126 86 3 15 Skutskär UT 92 55 52 12 17 13 14 594 81 131 49 9 Skutskär UT 64 44 26 11 9 5 7 800 84 50 10 6 Snow dump 202 58 48 0 1 0 0 439 310 106 0 23 ST airport, east 98 33 41 1 1 1 1 42 88 93 4 16 ST airport, west 117 53 63 2 0 1 19 131 143 116 0 15 Storvreta 116 21 34 5 1 1 3 105 118 98 2 13 Sörtuna 84 72 76 2 7 0 8 180 104 89 14 13 Uppsala 115 21 56 0 0 0 3 112 140 97 1 29 stormwater pond Vivsta 105 22 37 2 7 0 0 15 13 56 10 6 Volvo 170 97 17 29 31 14 0 29 36 41 66 55 Volvo 170 58 61 13 19 16 0 49 32 80 45 19 Ärna 128 45 48 2 1 1 11 234 130 100 1 24 Skebäcksdammen 76 29 37 3 1 0 3 258 130 35 0 10 TABLE A2 RECOVERY (%) OF INTERNAL STANDARDS (IS) IN FILTER SAMPLES. M-BDE47 M-BDE99 M-BDE100 M-BDE153 M-BDE154 M-BDE183 M-BDE209 M-TNBP M-TPHP M-HBB M-EHTBB M-aDDC-CO Essingeleden 166 102 124 48 46 57 16 30 48 243 83 20 Field blank 78 87 89 98 98 104 62 0 1 90 91 110 Field blank 60 75 71 72 78 76 43 2 7 71 67 95 Field blank 74 83 80 85 91 99 79 1 12 83 82 100 Field blank 71 78 77 84 87 94 111 0 3 84 79 110 Field blank 63 75 76 84 88 87 62 8 19 60 78 100 Fläskebo 64 61 67 62 75 80 65 2 10 71 68 79 Fortum 81 76 70 50 57 90 509 58 51 122 72 84 Halmsjöbäcken 116 81 93 29 86 54 65 10 26 105 64 64 Henriksdal (flow-int) 288 237 265 249 284 192 348 100 189 384 242 205 Henriksdal (grab) 81 72 82 77 69 37 62 26 33 128 76 29 Hovgården 94 63 61 35 58 82 316 73 44 134 46 138 Hovgården 105 66 68 40 61 85 454 17 19 131 69 183 Högbytorp 60 59 58 54 55 80 131 4 12 62 68 63 Högbytorp recipient 43 60 38 68 49 80 2 2 17 57 74 50 Issjöbäcken 80 75 73 74 77 76 93 8 27 104 73 86 Issjön 107 36 62 95 83 69 135 4 26 146 47 108 Järnbrottsdammen 41 32 37 29 36 32 76 1 11 60 34 43 Järnbrottsdammen 82 72 76 77 80 71 128 8 23 115 76 85 Kungsängsverket 129 97 116 19 130 102 132 59 49 122 104 118 Kungsängsverket 117 107 114 34 128 107 136 1 9 120 110 126 Lab blank 89 87 99 102 112 106 123 0 1 105 93 134 Nyköpingsån 83 75 18 66 76 32 113 2 24 106 81 35 Ryaverket 94 92 111 92 85 38 2 59 43 111 98 15 Shooting range 74 76 80 79 79 63 57 0 3 90 77 86 Skavsta 83 107 66 107 103 180 1051 105 18 126 89 316 Skavsta 149 107 78 87 98 224 0 0 2 97 88 298 Skebäcksdammen 86 62 65 41 45 57 117 0 3 132 64 59 Skebäcksverket 80 62 76 48 73 48 104 2 15 112 66 46 Skutskär IN 70 77 67 82 86 82 61 10 28 86 79 92 Skutskär OUT 74 68 66 70 86 39 2 28 24 119 71 40 Skutskär OUT 79 72 80 76 83 52 62 11 22 107 84 60 Snow dump 62 57 49 52 44 28 1.8 8.6 20 76 67 31 ST airport, east 95 92 90 92 98 73 112 0 15 124 97 93 ST airport, west 86 64 71 52 46 29 96 19 42 120 69 42 Storvreta 73 52 6 65 69 45 75 3 21 91 57 63 Sörtuna 80 78 82 52 87 79 79 0 7 91 83 95 Uppsala stormwater pond 70 48 42 37 38 72 221 11 12 121 49 78 Vivsta 0 123 34 53 51 148 0 0 8 0 5 184 Volvo 84 70 77 90 91 112 132 4 23 112 73 102 Volvo 86 58 74 89 89 107 101 2 20 110 62 80 Ärna 65 64 70 74 78 78 73 0 6 77 67 104 Table A3 Concentrations (>MDL, ng L-1) of HFRs and PBDEs in water phase samples. 246TBP BB-153 PBB-Acr PBT TBBPA TBX TCBPA BDE47 BDE66 BDE99 BDE100 BDE209 Halmsjöbäcken Fläskebo Järnbrottsdammen Järnbrottsdammen 330 a Skebäcksverket Skebäcksdammen Fortum Sörtuna Nyköpingsån Skavsta Skavsta Kungsängsverket Shooting range Högbytorp 230 a Högbytorp recipient Skutskär IN Skutskär OUT Skutskär OUT Essingeleden Henriksdal (flow-int) Henriksdal (grab) Storvreta Uppsala stormwater pond Snow dump ST airport, west ST airport, east Vivsta Ärna 370 b Volvo Volvo 280 a Hovgården Hovgården Issjön Ryaverket Issjöbäcken Kungsängsverket Lab blank Table A4 Concentrations (>MDL, ng L-1) of OPFRs in water phase samples. BADP EHDPP mTMPP oTMPP pTMPP RDP TBOEP TBPP TCEP TCIPP TDCIPP TEHP TIBP TiPPP TNBP TPHP TTBNPP Halmsjöbäcken Fläskebo Järnbrottsdammen Järnbrottsdammen Skebäcksverket 61 Skebäcksdammen 73 260 Fortum Sörtuna Nyköpingsån Skavsta 9900 5.6 16 Skavsta 23000 Kungsängsverket 21 a Shooting range 55000 a,b Högbytorp 21 2.9 Högbytorp recipient Skutskär IN Skutskär OUT Skutskär OUT Essingeleden Henriksdal (flow-int) Henriksdal (grab) Storvreta 23 120 Uppsala stormwater pond 140 74 Snow dump ST airport, west ST airport, east Vivsta 4400 6.2 0.016 Ärna Volvo Volvo Hovgården Hovgården Issjön Ryaverket 17 12 Issjöbäcken Kungsängsverket Lab blank Table A5 Concentrations (>MDL, ng L-1) of HFRs and PBDEs in particulate phase samples. 246TBP ATE PBB-Acr PBT sDDC-CO TBBPA TCBPA BDE47 BDE66 BDE85 BDE99 BDE100 BDE153 BDE154 BDE183 Halmsjöbäcken 1.0 Fläskebo 38 a Järnbrottsdammen 7.7 a Järnbrottsdammen 2.5 a Skebäcksverket Skebäcksdammen 5.0 a Fortum 0.43 Sörtuna 27 a Nyköpingsån 0.48 a Skavsta 7.4 a Skavsta 25 Kungsängsverket Shooting range 8.2 a Högbytorp 16 a Högbytorp recipient Skutskär IN Skutskär OUT 4.2 Skutskär OUT Kungsängsverket Essingeleden 1.2 0.047 Henriksdal (grab) Henriksdal (flow-int) Uppsala stormwater pond 20 a Snow dump ST flygplats, west ST airport, east 3.4 a Vivsta 57 a Ärna Volvo 130 a Volvo 80 a Storvreta 7.2 a Hovgården Hovgården Issjön 0.23 a Ryaverket Issjöbäcken Lab blank Table A6 Concentrations (>MDL, ng L-1) of OPFRs in particulate samples. BADP EHDPP mTMPP oTMPP RDP TBOEP TBPP TCEP TCIPP TDCIPP TEHP TiPPP TNBP TPHP TTBNPP Halmsjöbäcken Fläskebo Järnbrottsdammen Järnbrottsdammen Skebäcksverket 0.027 0.030 Skebäcksdammen Fortum 0.037 0.019 Sörtuna Nyköpingsån Skavsta Skavsta Kungsängsverket Shooting range 0.025 a