NEW ORGANIC POLLUTANTS IN AIR, 2007

Transcription

1 Norwegian pollution monitoring programme SPFO report 1077/2010 NEW ORGANIC POLLUTANTS IN AIR, 2007 TA Project carried out by the Norwegian Institute for Air Research

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3 Preface This report is an English translation of the report Nye miljøgifter i luft 2007, which was published by the Norwegian Pollution Control Authority (SFT) in 2008 (SPFO report 1031/2008, TA-2418/2008). SFT changed its name to the Climate and Pollution Agency in January The report presents measurements of concentrations of two new groups of organic pollutants, brominated flame retardants and polyfluorinated substances, at the background stations Birkenes in Southern Norway and Zeppelin at Ny-Ålesund in Svalbard. The properties of these substances suggest a potential for long-range atmospheric transport to remote areas, and it is therefore of interest to study their concentrations in air both on the Norwegian mainland and in Norwegian territory in the Arctic. This study was carried out as a supplement to the monitoring programme for organic pollutants run by the Norwegian Institute for Air Research for the Climate and Pollution Agency as part of the Comprehensive Atmospheric Monitoring Programme (CAMP) under the OSPAR Commission (trace elements and organic compounds at Birkenes) and the Arctic Monitoring and Assessment Programme (AMAP) (organic compounds and trace elements at Zeppelin, Ny-Ålesund). We would like to thank the former SFT for funding the project, Tor Johannessen for the interest he has shown in this new element of the monitoring programme for organic air pollutants, and Alison Coulthard for translating the report into English. Many people have contributed to the preparation of this report at every stage from sampling and technical maintenance to chemical analysis, quality assurance, data analysis and library services. We would particularly like to thank Kristine Aasarød for her expert help in producing the final document. Kjeller, 29 June 2010 Stein Manø Project manager, Norwegian Institute for Air Research 2

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5 Contents 1. Summary Sampling Background stations Birkenes Zeppelin station, Ny-Ålesund Sampling equipment Chemical analysis Substances analysed Extraction and sample preparation Quantification Properties of the compounds analysed Brominated flame retardants Polyfluorinated substances Results Brominated compounds Polyfluorinated substances Calculation of air mass trajectories Discussion Brominated compounds Polyfluorinated substances References Appendix A Raw data

6 1. Summary In addition to the classical persistent organic pollutants (POPs) of the 1960s and 1970s which include chlorinated pesticides such as DDT and hexachlorocyclohexane (HCH), and substances manufactured for technical uses, like polychlorinated biphenyls (PCBs), new substances showing similar levels of persistence and toxicity have lately been detected in environmental samples. These new substances were taken into use after the classical POPs were banned or phased out. Many of these newer substances are in use, and some are still being manufactured. They include brominated flame retardants and polyfluorinated substances. A number of publications have documented bioaccumulation of these substances, including in samples from the Arctic. Published data on new organic pollutants in air is much more limited. It is thus of great interest to investigate background levels of these substances in air both in mainland Norway and in Norwegian territory in the Arctic. The report describes the second measurement series for brominated flame retardants and polyfluorinated substances from the background stations Birkenes in Southern Norway and Zeppelin at Ny-Ålesund in Svalbard, where routine monitoring of background levels of organic pollutants in air in Norway is carried out. A new high volume sampler has been developed for brominated flame retardants. After sampling, the samples were analysed by the Norwegian Institute for Air Research at its laboratories at Kjeller (near Oslo) and in Tromsø (north Norway). Brominated substances were investigated in both the gas phase and the particulate phase, and included polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). Only the particle-bound components of polyfluorinated substances were studied. The pollutant levels were low, as expected, and there were generally no clear differences between the levels at the two background stations. The toxic and persistent polyfluorinated substances for which there is most published material are perfluorooctyl sulfonate (PFOS) and perfluorooctanoic acid (PFOA). Significant quantities of both PFOA and PFOS were found in almost all the samples. The report includes data on all the pollutants in these groups that were detected, back trajectory plots for samples with high and low values for specific groups of substances, and comparisons with data from the literature. Raw data for all the samples are presented in the appendix. 5

7 2. Sampling 2.1 Background stations Birkenes Birkenes is part of the Norwegian monitoring network for background levels of air pollutants. It has been operating since 1971, and in 2004 it was upgraded with sampling equipment for organic pollutants such as pesticides and PCBs when the station at Lista on the south coast was closed down. Monitoring of organic pollutants at Birkenes is commissioned by the Climate and Pollution Agency, and the results are reported to the Comprehensive Atmospheric Monitoring Programme (CAMP), which is one of the activities included in the OSPAR Commission s studies of inputs of pollution from land-based sources to the North- East Atlantic. Birkenes is in Aust-Agder county, well away from local sources of pollution, and about 30 km north-east of Kristiansand (altitude 190 m, position 58 23' N, 8 15' E). Its location makes it a very suitable site for monitoring background levels of pollution Zeppelin station, Ny-Ålesund This background station is in the Svalbard archipelago, a short distance outside Ny-Ålesund on the west coast of Spitsbergen. It is on the mountain Zeppelinfjellet at an altitude of 474 m. (position N, 11 88' E). Organic pollutants have been monitored continuously at this station since 1993, as part of the Arctic Monitoring and Assessment Programme (AMAP). Local pollution sources only have a significant effect on the results in special circumstances, since the station lies above the inversion layer. This is a highly suitable site for monitoring atmospheric pollution. 2.2 Sampling equipment A high volume sampler developed specially for this project by the Swiss firm Digitel was used to sample brominated compounds. Electrical equipment both at the background stations and in the laboratory may contain relatively volatile brominated compounds, and it was therefore considered important to construct the equipment in way that would minimise the risk of sample contamination, particularly since it was clear that the levels of pollutants to be measured would be low. The same applied to the glass equipment used for extraction in the laboratory. The sampler and extraction equipment are described in more detail in Manø et al Since only particle-bound components of polyfluorinated substances were sampled, the risk of contamination was lower, and it was decided to use the high-volume air samplers that have been used at the background stations for many years. 6

8 3. Chemical analysis LC-MS and GC-MS were used to detect TBA and specific PBBs, PBDEs, HBCDs and PFAS in the samples. 3.1 Substances analysed Table 3.1 lists the substances that were analysed in this study. Table 3.1. Substances analysed, showing abbreviation, full name and detection technique used. Abbreviation Full name Detection technique TBA 2,4,6-Tribromoanisol GC-MS PBB-15 4,4 -Dibromobiphenyl GC-MS PBB-153 2,2 4,4,5,5- Hexabromobiphenyl GC-MS PBDE-28 2,4,4 -Tribromodiphenyl ether GC-MS PBDE-47 2,2,4,4 -Tetrabromodiphenyl ether GC-MS PBDE-49+PBDE-71 2,2,4,5 -and 2,3,4,6- Tetrabromodiphenyl ether GC-MS PBDE-66 2,3,4,4 - Tetrabromodiphenyl ether GC-MS PBDE-77 3,3,4,4 - Tetrabromodiphenyl ether GC-MS PBDE-85 2,2,3,4,4 -Pentabromodiphenyl ether GC-MS PBDE-99 2,2,4,4,5- Pentabromodiphenyl ether GC-MS PBDE-100 2,2,4,4,6- Pentabromodiphenyl ether GC-MS PBDE-119 2,3,4,4,6- Pentabromodiphenyl ether GC-MS PBDE-138 2,2,3,4,4,5 -Hexabromodiphenyl ether GC-MS PBDE-153 2,2,4,4,5,5 - Hexabromodiphenyl ether GC-MS PBDE-154 2,2,4,4,5,6 - Hexabromodiphenyl ether GC-MS PBDE-183 2,2,3,4,4,,5,6-Heptabromodiphenyl ether GC-MS PBDE-196 2,2,3,3,4,4,5,6 -Octabromodiphenyl ether GC-MS PBDE-206 2,2,3,3,4,4,5,5,6-Nonabromodiphenyl ether GC-MS PBDE-209 Decabromodiphenyl ether GC-MS α-hbcd α- Hexabromocyclododecane HPLC-MS β-hbcd β- Hexabromocyclododecane HPLC-MS γ-hbcd γ- Hexabromocyclododecane HPLC-MS 6:2 FTS 1H,1H,2H,2H-Perfluorooctane sulfonate HPLC-MS PFOSA Perfluorooctane sulfonamide HPLC-MS PFBS Perfluorobutane sulfonate HPLC-MS PFHxS Perfluorohexane sulfonate HPLC-MS PFOS Perfluorooctane sulfonate HPLC-MS PFDcS Perfluorodecane sulfonate HPLC-MS PFBA Perfluorobutanoic acid HPLC-MS PFHxA Perfluorohexanoic acid HPLC-MS PFHpA Perfluoroheptanoic acid HPLC-MS PFOA Perfluorooctanoic acid HPLC-MS PFNA Perfluorononanoic acid HPLC-MS PFDcA Perfluorodecanoic acid HPLC-MS PFUnA Perfluoroundecanoic acid HPLC-MS 7

9 3.2 Extraction and sample preparation The samples (glass-fibre filters and gas-phase adsorbent) for analysis of brominated compounds were stored at +4 C prior to analysis. The gas-phase adsorbent consisted of two polyurethane foam plugs in a glass column with a flat ground-glass joint at each end. An isotope-labelled internal standard was added to this system before it was mounted in an extraction apparatus constructed specifically for the project and extracted for 4 h with 10% diethyl ether in hexane. The glass-fibre filter was extracted separately for 8 h with diethyl ether in hexane. The extracts were combined and concentrated before treatment with sulphuric acid and clean-up on 4 g activated silica. After volume reduction to 100 µl, a recovery standard was added. The samples (glass-fibre filters) for analysis of fluorinated compounds were stored at -18 C prior to analysis. An isotope-labelled internal standard was added to the filter before extraction twice with ammonium acetate in methanol using ultrasound. After volume reduction, clean-up on carbon and centrifuging, a recovery standard was added. 3.3 Quantification TBA, PBBs and PBDEs were analysed by gas chromatography/electron impact highresolution mass spectrometry (GC/HRMS). Table 3.1 lists the PBBs and PBDEs that were detected. Quantification was against BDE-28, -47, -99, -153, -183 and -209 in the isotopelabelled internal standard. An aliquot of the sample extract was withdrawn and the solvent replaced with methanol. This sample was analysed for α-,β- and γ-hbcd by liquid chromatography/electrospray ionisation low-resolution mass spectrometry (LC/MS-ESI). Quantification was against α- and γ-hbcd in the isotope-labelled internal standard. PFAS were analysed by reverse phase liquid chromatography combined with time-of-flight mass spectrometry. Table 3.1 lists the compounds analysed. 8

10 4. Properties of the compounds analysed 4.1 Brominated flame retardants There are five main types of brominated flame retardants: brominated bisphenols, diphenyl ethers, cyclododecanes, phenols and phthalic acid derivatives, and the first three groups represent the greatest production volume. The molecular structure of PBDEs is similar to that of PCBs, and they are numbered correspondingly in the IUPAC (International Union of Pure and Applied Chemistry) system. Like PCBs, PBDE mixtures may contain up to 209 different congeners, which differ in the number and position of the bromine atoms in the molecule. In practice, commercial mixtures consist of far fewer congeners, because many congeners are unstable and tend to debrominate. The same phenomenon has been observed for PBBs (Birnbaum and Staskal 2004). Three commercial PBDE mixtures have been used. Decabromodiphenyl ether (DBDE, or decabde) consists of >97 % BDE 209, < 3% nonabde and a small proportion of octabde. It is used as a flame retardant in electrical equipment and textiles. Commercial octabde is a more complex mixture, consisting of several congeners: 10-12% hexabde, 44% heptabde, 31-35% octabde, 10-11% nonabde and < 1% decabde. OctaBDE makes up a small proportion of the total volume of BPDEs, and has been used as an additive in plastics. The third commercial product, pentabde or pentabrom, is a viscous liquid that was used in textiles and as an additive in polyurethane foams, where this flame retardant could account for up to 30% of the weight (Hale 2002). There is variation in the composition of commercial pentabde, but it generally consists of 24-38% tetrabde, 50-60% pentabde and 4-8% hexabde. The main congeners are IUPAC numbers 47 (tetrabde), 99 and 100 (pentabdes) and 153 and 154 (hexabdes). BDEs 47 and 99 make up about 75% of the total mass, with roughly twice as much 99 as 47. PBDEs used as flame retardants are not chemically bound to the products to which they are added, and can therefore gradually leach to the surroundings. PBDEs are very stable, but it has been observed that they can debrominate under UV light, and that these reactions proceed more rapidly in higher brominated compounds than for those containing fewer bromine atoms (Eriksson et al., 2001; Söderström et al., 2004). PentaBDE is the only product that appears to be persistent and show a tendency to bioaccumulate (Betts, 2002). Like PCBs, PBDEs accumulate in fatty tissue, and tetrabde and pentabde appear to be the components that are most toxic and show the highest tendency to bioaccumulate (Siddiqi, 2003). HBCD is a non-aromatic cyclic alkane that is primarily used as an additive in styrene-based plastics. It has also been used to a lesser extent in textile coatings, cables, latex binders and unsaturated polyesters. Commercial HBCD consists of three isomers, α, β and γ-hbcd, and the main component is γ-hbcd. HBCD is persistent, toxic, bioaccumulative and may constitute a threat to the environment (Betts, 2003). 9

11 4.2 Polyfluorinated substances The term PFAS refers to a group of organic substances used for surface treatment of textiles and in polymers, fire fighting foams and insecticides. Several substances show a potential for bioaccumulation and toxic effects, and are persistent. Large volumes of PFAS have been manufactured for several decades, and they have been widely used to impregnate a variety of products and make them stain-, oil- and water-repellent. PFOS and PFOA are the compounds that have been most thoroughly investigated so far. The largest manufacturer has voluntarily phased out the production of PFOS-based chemicals, but substances containing poly- or perfluorinated carbon chains are still in use, for example fluorotelomer alcohols (Jahnke et al. 2007). 10

12 5. Results Results are only presented for those substances that were detected at levels significantly higher than the field blank values. Many of the fluorinated compounds in particular were below the detection limits in many of the samples. 5.1 Brominated compounds TBA Table 5.1 shows measurements of TBA in air at both background stations. Table 5.1. Concentrations of TBA in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m g Field blank 0.01 Field blank 0.12 Mean 4.95 Mean 7.72 Minimum 2.33 Minimum 4.02 Maximum 9.78 Maximum Field blank not used in calculations of mean, minimum and maximum values. g: Low recovery of internal standard 11

13 PBDE-28 Table 5.2 shows measurements of PBDE-28 in air at both background stations. Table 5.2. Concentrations of PBDE-28 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m i i Field blank 0.02 Field blank <0.01 Mean 0.05 Mean 0.03 Minimum 0.02 Minimum 0.01 Maximum 0.10 Maximum 0.07 Field blank not used in calculations of mean, minimum and maximum values. i: Interference 12

14 PBDE-47 Table 5.3 shows measurements of PBDE-47 in air at both background stations. Table 5.3. Concentrations of PBDE-47 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m i Field blank 0.69 Field blank 0.10 Mean 0.51 Mean 0.75 Minimum 0.16 Minimum 0.20 Maximum 1.35 Maximum 2.40 Field blank not used in calculations of mean, minimum and maximum values. i: Interference 13

15 Sum PBDE-49 and PBDE-71 Table 5.4 shows measurements of sum PBDE-49 and PBDE-71 in air at both background stations. Table 5.4. Concentrations of sum PBDE-49 and PBDE-71 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m i < i < Field blank <0.01 Field blank <0.01 Mean 0.04 Mean 0.04 Minimum 0.01 Minimum 0.01 Maximum 0.08 Maximum 0.14 Field blank not used in calculations of mean, minimum and maximum values. i: Interference 14

16 PBDE-66 Table 5.5 shows measurements of PBDE-66 in air at both background stations. Table 5.5. Concentrations of PBDE-66 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m i i < < < i < < < i < i i <0.01 Field blank <0.01 Field blank <0.01 Mean 0.03 Mean 0.03 Minimum 0.01 Minimum 0.01 Maximum 0.08 Maximum 0.05 Field blank not used in calculations of mean, minimum and maximum values. i: Interference 15

17 PBDE-85 Table 5.6 shows measurements of PDBE-85 in air at both background stations. Table 5.6. Concentrations of PBDE-85 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m < < < < < < < < < < < < < < i < < < < < i < < i < <0.01 Field blank <0.01 Field blank <0.01 Mean 0.02 Mean 0.02 Minimum 0.01 Minimum 0.01 Maximum 0.03 Maximum 0.05 Field blank not used in calculations of mean, minimum and maximum values. i: Interference 16

18 PBDE-99 Table 5.7 shows measurements of PBDE-99 in air at both background stations. Table 5.7. Concentrations of PBDE-99 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m g g g g g g g g g g Field blank 0.18 Field blank 0.06 Mean 0.38 Mean 0.32 Minimum 0.15 Minimum 0.06 Maximum 1.38 Maximum 1.60 Field blank not used in calculations of mean, minimum and maximum values. g: Low recovery of internal standard 17

19 PBDE-100 Table 5.8 shows measurements of PBDE-100 in air at both background stations. Table 5.8. Concentrations of PBDE-100 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m g Field blank 0.19 Field blank 0.02 Mean 0.09 Mean 0.08 Minimum 0.03 Minimum 0.02 Maximum 0.33 Maximum 0.39 Field blank not used in calculations of mean, minimum and maximum values. g: Low recovery of internal standard 18

20 PBDE-153 Table 5.9 shows measurements of PBDE-153 in air at both background stations. Table 5.9. Concentrations of PBDE-153 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m i i g g g g g < < g g < < < g g g < < < < i i Field blank 0.04 Field blank <0.01 Mean 0.06 Mean 0.04 Minimum 0.01 Minimum 0.02 Maximum 0.19 Maximum 0.12 Field blank not used in calculations of mean, minimum and maximum values. i: Interference g: Low recovery of internal standard 19

21 PBDE-154 Table 5.11 shows measurements of PBDE-154 in air at both background stations. Table Concentrations of PBDE-154 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m < < g < < < i < < i i <0.01 Field blank 0.05 Field blank <0.01 Mean 0.03 Mean 0.04 Minimum 0.01 Minimum 0.01 Maximum 0.13 Maximum 0.12 Field blank not used in calculations of mean, minimum and maximum values. i: Interference g: Low recovery of internal standard 20

22 PBDE-183 Table 5.11 shows measurements of PBDE-183 in air at both background stations. Table Concentrations of PBDE-183 in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m < i < g < < g g g g < g g g g g < g < g g i g g < < <0.01 Field blank <0.01 Field blank <0.01 Mean 0.02 Mean 0.02 Minimum 0.02 Minimum 0.02 Maximum 0.03 Maximum 0.02 Field blank not used in calculations of mean, minimum and maximum values. i: Interference g: Low recovery of internal standard 21

23 Sum PBDE-28, PBDE-47, PBDE-49+71, PBDE-66, PBDE-85, PBDE-99, PBDE-100, PBDE-153, PBDE-154 and PBDE-183 Table 5.12 shows measurements of sum PDBE (the following congeners: 28, 47, 49, 66, 71, 85, 99, 100, 119, 153, 154 and 183) in air at both background stations. Table Concentrations of sum PBDE 28, 47, 49, 66, 71, 85, 99, 100, 153, 154 and 183 in air at both background stations. From Birkenes To Sum PBDE (pg/m 3 ) From Zeppelin To Sum PBDE (pg/m 3 ) i/g Field blank 1.01 Field blank 1.21 Mean 0.39 Mean 0.33 Minimum 3.36 Minimum 4.70 i: Interference g: Low recovery of internal standard 22

24 α-, β- and γ-hbcd Table 5.13 and Table 5.14 show measurements of α-, β- and γ-hbcd in air at both background stations. Table Concentrations of α-, β- and γ-hbcd in air at Birkenes. Birkenes α-hbcd β-hbcd γ-hbcd Sum HBCD From To pg/m 3 pg/m 3 pg/m 3 pg/m < < i < g 22.45i <0.26 < < < < <0.25 < i 0.10i < <0.15 < <0.08 < < < < i Field blank 0.49 < Mean Minimum Maximum Field blank not used in calculations of mean, minimum and maximum values. i: Interference g: Low recovery of internal standard Table Concentrations of α-, β- and γ-hbcd in air at Zeppelin. Zeppelin α-hbcd β-hbcd γ-hbcd Sum HBCD From To pg/m 3 pg/m 3 pg/m 3 pg/m < i 0.18i < < < < < < < < < < < i 0.07i <0.11 <0.07 <0.17 <0.34 Field blank 0.25 < Mean 1.86 nd Minimum 0.14 nd Maximum 4.94 nd Field blank not used in calculations of mean, minimum and maximum values. nd: not detected. i: Interference g: Low recovery of internal standard 23

25 5.2 Polyfluorinated substances PFOA Table 5.15 shows measurements of PFOA in air at both background stations. Table Concentrations of PFOA in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m < g < < < < < <0.29 Field blank < Mean Minimum Maximum 1.51 Field blank <0.16 Mean 1.04 Minimum 0.51 Maximum 3.02 Field blank not used in calculations of mean, minimum and maximum values. g: Low recovery of internal standard 24

26 PFOS Table 5.16 shows measurements of PFOS in air at both background stations. Table Concentrations of PFOS in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m < g < < Field blank Mean Minimum Maximum 0.97 Field blank 0.09 Mean 0.32 Minimum 0.04 Maximum 0.81 Field blank not used in calculations of mean, minimum and maximum values. g: Low recovery of internal standard 25

27 Sum PFOA and PFOS Table Concentrations of sum PFOA and PFOS in air at both background stations. Birkenes Zeppelin From To pg/m 3 From To pg/m g < Field blank Mean Minimum Field blank 0.91 Mean 0.04 Minimum 3.83 g: Low recovery of internal standard 26

28 6. Calculation of air mass trajectories Atmospheric trajectory models provide information on the origin of air parcels. This report uses back trajectory plots from the model FLEXTRA (Stohl et al., 1995; Stohl and Seibert, 1998), based on meteorological data from the European Centre for Medium-Range Weather Forecasts (ECMWF). Figure 6.1 shows an example of a back trajectory for air arriving at Birkenes on 15 August 2007 at 06:00 hours. The back trajectories are shown for a seven-day period, and for three different arrival altitudes at Birkenes, as shown in the key on the righthand side. Height above sea level (in metres) is indicated by the colour scale. Three-hour intervals are marked by smaller dots and 24-hour intervals by larger dots. The position error is estimated to be 20% of the distance travelled, but may in some cases be greater. FLEXTRA is solely a trajectory model, and does not take into account atmospheric processes such as degradation or dry or wet deposition. Figure 6.1. Example of a back trajectory plot from FLEXTRA. TBA Figure 6.2 shows back trajectory plots for air arriving at Birkenes on 22 November 2007 at 12:00 hours and 23 November 2007 at 00:00 hours, the period during which the sample with the highest concentration of TBA was taken. TBA was transported from Greenland/Iceland across the Atlantic and Western Europe and also from south-western Europe and the UK across the Skagerrak to Birkenes. Figure 6.3 shows trajectories for the Birkenes sample with the lowest TBA concentration, which was transported from northern and western Canada across the Atlantic and the southernmost part of Norway to Birkenes. 27

29 Figure 6.2. Back trajectories for the sample with the highest TBA concentration taken at Birkenes. Figure 6.3. Back trajectories for the sample with the lowest TBA concentration taken at Birkenes. Figure 6.4 shows back trajectories for air arriving at Zeppelin in the period when the sample with the highest TBA concentration was taken, August The air masses were transported from northern Russia and the Arctic Ocean. Figure 6.5 shows back trajectories for the sample from Zeppelin with the lowest TBA concentration, in air from northern parts of Norway, Finland and Russia. 28

30 Figure 6.4. Back trajectories for the sample with the highest TBA concentration taken at Zeppelin. Figure 6.5. Back trajectories for the sample with the lowest TBA concentration taken at Zeppelin. 29

31 Sum PBDE: PBDE-28, PBDE-47, PBDE-49+71, PBDE-66, PBDE-85, PBDE-99, PBDE- 100, PBDE-153, PBDE-154 and PBDE-183 Figure 6.6 shows back trajectories for air arriving at Birkenes in the period September 2007, the period during which the sample with the highest Sum PDBE concentration was taken. The trajectory was partly from the east coast of Canada, across the Atlantic and via Ireland and the UK, and partly from Greenland and the Arctic Ocean and across mid-norway and southern Norway. Figure 6.7 shows back trajectories for the Birkenes sample with the lowest Sum PBDE concentration, which was transported from Greenland and Iceland and across the southern part of Norway. Figure 6.6. Back trajectories for the sample with the highest Sum PBE concentration taken at Birkenes. Figure 6.7. Back trajectories for the sample with the lowest Sum PBE concentration taken at Birkenes. Figure 6.8 shows back trajectories for air arriving at Zeppelin in the period when the sample with the highest Sum PBDE concentration was taken, August The air masses were transported from northern Russia and the Arctic Ocean. 30

32 Figure 6.9 shows back trajectories for the sample from Zeppelin with the lowest Sum PBDE concentration, in air transported from Greenland and the Arctic Ocean. Figure 6.8. Back trajectories for the sample with the highest Sum PBDE concentration taken at Zeppelin. Figure 6.9. Back trajectories for the sample with the lowest Sum PBDE concentration taken at Zeppelin. 31

33 Sum HBCD Figure 6.10 shows back trajectories for air arriving at Birkenes in the period when the sample with the highest Sum HBCD concentration was taken, 1-3 August The air masses were transported largely from the East Atlantic, across Ireland and the UK, and across the North Sea. Figure 6.11 shows back trajectories for the Birkenes sample with the lowest Sum HBCD concentration, which was transported from the North Atlantic and the Arctic Ocean across Norway and Sweden. Figure Back trajectories for the sample with the highest Sum HBCD concentration taken at Birkenes. Figure Back trajectories for the sample with the lowest Sum HBCD concentration taken at Birkenes. Figure 6.12 shows back trajectories for air arriving at Zeppelin in the period when the sample with the highest Sum HBCD concentration was taken, November The air masses were transported from northern Canada, Greenland and the Arctic Ocean, and from northeastern Europe. Figure 6.13 shows back trajectories for the sample from Zeppelin with the lowest Sum HBCD concentration, in air transported mainly from the Arctic Ocean. 32

34 Figure Back trajectories for the sample with the highest Sum HBCD concentration taken at Zeppelin. Figure Back trajectories for the sample with the lowest Sum HBCD concentration taken at Zeppelin. 33

35 Sum PFOA and PFOS Figure 6.14 shows back trajectories for air arriving at Birkenes in the period December 2007, the period during which the sample with the highest Sum PFOA and PFOS concentration was taken. The air was transported from the US and Canada to Greenland, Ireland and the UK. Figure 6.15 shows back trajectories for one of the two Birkenes samples with the lowest Sum PFOA and PFOS concentration, in air transported from the East and North Atlantic across Scotland and the North Sea. Figure Back trajectories for the sample with the highest Sum PFOA and PFOS concentration taken at Birkenes. Figure Back trajectories for the sample with the lowest Sum PFOA and PFOS concentration taken at Birkenes. Figure 6.16 shows back trajectories for air arriving at Zeppelin in the period when the sample with the highest Sum PFOA and PFOS concentration was taken, 31 October-2 November The air was transported from northern Canada, Greenland and northern Russia. Figure 6.17 shows back trajectories for the sample from Zeppelin with the lowest Sum PFOA and PFOS concentration, in air mainly from Russia via the North Pole. 34

36 Figure Back trajectories for the sample with the highest Sum PFOA and PFOS concentration taken at Zeppelin. Figure Back trajectories for the sample with the lowest Sum PFOA and PFOS concentration taken at Zeppelin. 35

37 7. Discussion 7.1 Brominated compounds TBA Tribromanisol was found in air samples at both background stations, and the results are summarised in Table 7.1. Table 7.1. Key results for TBA in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements Mean 2006: 12.8 and 7.56 pg/m 3. TBA has previously been detected in marine samples (Schlabach et al., 2002; Vetter and Stoll, 2002), and it is assumed to be mainly a natural brominated compound that originates from marine microorganisms; however, it may also be of anthropogenic origin (Vetter and Stoll, 2002). There is little data on the substance from environmental samples. Because it behaves like a persistent organic compound and has structural similarities with other brominated compounds, monitoring of TBA levels has been recommended (Schlabach et al., 2002). Führer and Ballschmiter (1998) measured TBA during a cruise from Bremerhaven to Cape Town, and found concentrations in the range pg/m 3. The highest levels were measured in the northern hemisphere, and the sample with the highest concentration was taken at 13 N west of Senegal. A relatively high concentration (30 pg/m 3 ) was also found west of Portugal. TBA levels measured in samples from both Birkenes and Zeppelin were lower than those found by Führer and Ballschmiter, and lower at Birkenes than at Zeppelin. TBA was above the detection limit in all samples in the present study. There was little change in the level at Zeppelin from 2006, whereas levels were lower at Birkenes in 2007 than the year before. Back trajectories calculated for the samples with the highest and the lowest concentrations of TBA showed transport across both sea and densely populated areas in both cases. The results of Führer and Ballschmiter and those of the present study are not incompatible, and it is likely that TBA is largely of natural origin. It is not possible conclude whether TBA levels are showing any trend from the data available. PBB-153 2,2,4,4,5,5 -Hexabromobiphenyl was found in very low concentrations in samples from both stations in 2006, but was not detected in the samples taken in The production of technical hexabb mixtures was banned in the US and Europe in 1973, and production of decabb ceased in An earlier study of brominated flame retardants and chlorinated paraffins (Schlabach et al. 2002) included measurements of levels of PBB-15, PBB-49 and PBB-52 in the moss Hylocomium splendens, which is used as a biomonitor of the deposition of POPs from air. Since these substances have been phased out and no high concentrations were found, there is probably no reason to focus too much on them. However, 36

38 they can easily be analysed together with PBDE at little additional cost, so that their inclusion in future measurement series can be considered. PBDE Quantification of 17 different polybrominated diphenyl ethers was attempted for all samples. It proved possible to obtain clearly significant results for 11 of these relative to the detection limits and field blank values. The results are summarised in Table 7.2. Table 7.2. Key results for PBDE in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements BDE BDE BDE BDE BDE BDE BDE BDE BDE BDE The concentrations measured were generally low, less than 1 pg/m 3 for individual substances, and levels at the two stations were equally low. Sum PBDE values (all quantified congeners in all samples) are shown in Figure 7.1 for Birkenes and Figure 7.2 for Zeppelin. The heaviest congeners, PBDE-196 (octabde), 206 (nonabde) and 209 (decabde) were not detected in significant quantities relative to the detection limits and field blank values. PBDE- 119 was not detected in the 2007 samples. 37

39 Figure 7.1. Sum PBDE in all samples at Birkenes [pg/m 3 ]. 5,0 4,5 4,0 3,5 3,0 2,5 2,0 1,5 1,0 0,5 0, Figure 7.2. Sum PBDE in all samples at Zeppelin [pg/m 3 ]. 38

40 Figure 7.3 and Figure 7.4 show the distribution patterns for PBDE-28, 47, 99, 100 and 153 in sum PDBE in all samples from Birkenes and Zeppelin respectively. The patterns are very similar to those for the 2006 data set from the same stations (Manø et al. 2008). The dominant component of sum PDBE was PBDE-47 (a tetrabromodiphenyl ether), and most of the total consisted of PBDE-47 and PBDE-99 (a pentabromodiphenyl ether). The two heaviest congeners in this group made up a somewhat smaller proportion of the total at Zeppelin than at Birkenes. One explanation may be that the heavier congeners have less potential for longrange transport to areas as remote from pollution sources as the Arctic. Moreover, the heavy PDBEs debrominate on exposure to sunlight, and this is another possible explanation or contributory factor to the patterns found (Söderström et al., 2004). Debromination reduces levels of the heavier congeners such as decabde (PBDE-209), while levels of the lower PBDEs rise. The latter are more volatile, and are more easily transported to distant regions than the original compounds. Figure 7.5 shows the distribution patterns for the same PDBE congeners in samples taken at the monitoring station Kise (near Lake Mjøsa, Hedmark county) (Breivik et al., 2005). PBDE- 47 and PBDE-99 made up the bulk of the total in this case as well. Comparing this graph with the results from Zeppelin, makes it quite clear that levels of the heaviest PBDEs are lower in the Arctic than in areas near pollution sources or where background levels are higher. The same compounds also dominated in a study of air pollutants in the Great Lakes region of the US (Dodder et al., 2000). The commercial mixtures of brominated diphenyl ethers that have been most widely used are penta-, octo- and decabde, which contain five, eight and 10 bromine atoms respectively. Like all technical products, these are not pure substances, but mixtures. PentaBDE consists of 24-38% tetrabde, 50-60% pentabde and 4-8% hexabde. PBDE-47 and PBDE-99 make up about 75% of the total mass of pentabde (Birnbaum and Staskal, 2004). Some of the PDBE- 47 detected in the samples in the present study may, as mentioned earlier, have been formed by degradation of higher PBDEs. 100 % 90 % 80 % 70 % 60 % 50 % 40 % 30 % 20 % 10 % % Figure 7.3. Distribution patterns of Sum PBDE 28,47, 99, 100 and 153 at Birkenes. 39

41 Figure 7.4. Distribution patterns of Sum PBDE 28,47, 99, 100 and 153 at Zeppelin. 100% 80% 60% 40% 20% % 2 Sep 04 8 Sep Sep Sep Sep 04 5 Okt 04 x Okt Okt Okt 04 2 Nov 04 9 Nov Nov Nov Nov 04 7 Des Des Des Des 04 4 Jan Jan Jan Jan 05 Figure 7.5. Distribution patterns of PBDE 28, 47, 99, 100 and 153 in air samples at Kise (Breivik et al., 2005). PBDE-47 Table 7.3 summarises the results for PBDE-47. The mean values at the two stations were fairly similar, but somewhat higher at Zeppelin than at Birkenes, and the maximum value measured at Zeppelin was higher than that at Birkenes by a factor of about two. The mean value at Birkenes was the same as in 2006, while the mean at Zeppelin was higher in

42 Table 7.3. Key results for PBDE-47 in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements Mean 2006: 0.51 and 0.32pg/m 3. Table 7.4 shows measurements of PBDE-47 in air from various authors. The results from Birkenes and Zeppelin are low by comparison. This is probably because the North American measurements are more strongly influenced by local sources. There are major cities such as Chicago, Detroit and Toronto in the Great Lakes region contains large cities, which could explain the differences here. In addition, much higher concentrations have been found in samples from the Canadian Arctic (Alaee et al., 2003). The mean value in their samples from Alert and Tagish was higher than the concentration Strandberg et al. (2001) reported in air within the city of Chicago. It has been suggested that such high concentrations may be explained by a phenomenon that is not uncommon in Arctic and subarctic settlements in Canada uncontrolled open burning of waste. These results have been omitted from the table. A contribution of this kind from local sources can be ruled out in the samples in the present study. Table 7.4. Results for PBDE-47 in air. Station PBDE-47 concentration [pg/m 3 ] Reference South Ontario (rural) 2.97 Gouin et al Great Lakes Eagle Harbor 2.90 Strandberg et al Great Lakes Sturgeon Point 3.80 Strandberg et al Great Lakes Sleeping Bear Dunes 8.40 Strandberg et al Great Lakes 3.70 Dodder et al Ammarnäs (Lappland, Sweden) 6.30 Bergander et al Hoburgen (Gotland, Sweden) 0.70 Bergander et al Birkenes 0.51 Zeppelin 0.75 PBDE-99 Table 7.5 summarises the results for PBDE-99. The mean values for the two stations were low and very similar, but the minimum level at Zeppelin was lower than at Birkenes. The mean values were somewhat higher at both stations than the year before. Table 7.5. Key results for PBDE-99 in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements Mean 2006: 0.29 and 0.15 pg/m 3. Table 7.6 shows measurements of PBDE-99 in air from various authors. As mentioned before, the high levels in the North American samples are probably explained by the influence of urban areas in the Great Lakes region. The results from the present study are low by 41

43 comparison. The values at both background stations were very close to those found at Hoburgen at the southern tip of Gotland. Table 7.6. Results for PBDE-99 in air [pg/m 3 ]. Station PBDE-99 concentration [pg/m 3 ] Reference South Ontario (rural) 7.23 Gouin et al Great Lakes Eagle Harbor 2.1 Strandberg et al Great Lakes Sturgeon Point 3.8 Strandberg et al Great Lakes Sleeping Bear Dunes 5.3 Strandberg et al Great Lakes 3.6 Dodder et al Ammarnäs (Lappland, Sweden) 1.6 Bergander et al Hoburgen (Gotland, Sweden) 0.35 Bergander et al Birkenes 0.38 Zeppelin 0.32 PBDE-100 Table 7.7 summarises the results for PBDE-100. The mean values for the two background stations were low and of the same order of magnitude, but the mean was higher at Birkenes than at Zeppelin by a factor of three. The mean concentration at Birkenes was somewhat higher than the year before, while the mean at the Zeppelin station was unchanged. Table 7.7. Key results for PBDE-100 in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements Mean 2006: 0.06 and 0.03 pg/m 3. Table 7.8 shows various measurements of PBDE-100 in air taken from the literature. As mentioned before, the explanation for the high levels measured in the North American samples is probably that they are influenced by urban areas in the Great Lakes region. The results from Birkenes and the Zeppelin station are low by comparison. As in the case of PBDE-99, the values at both stations were very close to those found at Hoburgen at the southern tip of Gotland. Table 7.8. Results for PBDE-100 in air [pg/m 3 ]. Station PBDE-100 concentration [pg/m 3 ] Reference South Ontario (rural) 1.9 Gouin et al Great Lakes Eagle Harbor 0.29 Strandberg et al Great Lakes Sturgeon Point 0.39 Strandberg et al Great Lakes Sleeping Bear Dunes 0.80 Strandberg et al Great Lakes 0.33 Dodder et al Ammarnäs (Lappland, Sweden) 0.40 Bergander et al Hoburgen (Gotland, Sweden) 0.07 Bergander et al Birkenes 0.09 Zeppelin

44 PBDE-153 Table 7.9 summarises the results for PBDE-153. The mean values at the two stations were low, and the value at Birkenes was unchanged. The value at the Zeppelin station had risen, but the mean values for both 2006 and 2007 are based on a small number of measurements with a certain spread in the results, so the increase is not alarming. Levels of PBDE-153 were below the detection limit in most samples from both stations. Table 7.9. Key results for PBDE-153 in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements Mean 2006: 0.06 and 0.02 pg/m 3. Table 7.10 shows various measurements of PBDE-153 in air taken from the literature. As mentioned before, the explanation for the high levels measured in the North American samples is probably that they are influenced by urban areas in the Great Lakes region. The results from Birkenes and Zeppelin are low by comparison. For the higher PBDEs, there are few air measurement results for comparison. The levels measured in the present study were markedly lower than those from the Great Lakes region in the US/Canada, which is not surprising. Table Results for PBDE-153 in air [pg/m 3 ]. Station PBDE-153 concentration [pg/m 3 ] Reference Great Lakes Eagle Harbor 0.13 Strandberg et al Great Lakes Sturgeon Point 0.19 Strandberg et al Great Lakes Sleeping Bear Dunes 0.25 Strandberg et al Birkenes 0.06 Zeppelin 0.04 PBDE-154 Table 7.11 summarises the results for PBDE-154. The mean values from Birkenes and Zeppelin differed by a factor of two. The levels at both stations were very low, and at Zeppelin the concentration was below the detection limit in most of the samples. Table Key results for PBDE-154 in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements Mean 2006: 0.04 and 0.02 pg/m 3. Table 7.12 shows various measurements of PBDE-154 in air taken from the literature. As mentioned before, the explanation for the high levels measured in the North American samples is probably that they are influenced by urban areas in the Great Lakes region. The results from the present study are low by comparison. For the higher PBDEs, there are few air 43

45 measurement results for comparison. The levels measured in the present study were markedly lower than those from the Great Lakes region in the US/Canada, which is not surprising. Table Results for PBDE-154 in air [pg/m 3 ]. Station PBDE-154 concentration [pg/m 3 ] Reference Great Lakes Eagle Harbor 0,13 Strandberg et al Great Lakes Sturgeon Point 0,19 Strandberg et al Great Lakes Sleeping Bear Dunes 0,25 Strandberg et al Birkenes 0,03 Zeppelin 0,04 Summary PBDEs The levels measured in the present study were low compared with those that have been found in the Great Lakes region in the US/Canada, but in a number of cases comparable to those measured at Swedish background stations. There was little difference between PDBE levels at the two Norwegian background stations. Levels at Zeppelin were generally higher in 2007 than in Concentrations detected in air declined from the lighter to the heavier congeners, and PBDE- 209 was not detected in significant quantities. The two largest components of Sum PBDE were PBDE-47 and PBDE-99, a finding also made by other authors. These substances can debrominate when exposed to sunlight, forming more volatile products with greater long-range transport potential. The results suggest that PBDEs released by open burning of waste in the Arctic, in addition to long-range transport from more densely populated regions (source areas) may explain the levels that have been observed (Alaee et al., 2003; de Wit et al., 2004). There is nothing in the results of the present study to suggest that local sources in Ny-Ålesund interfere with measurements of PBDEs at Zeppelin. On the contrary, both the measured concentrations and the calculations of back trajectories indicate that the levels observed are explained by long-range transport from source areas. Gouin et al. (2002) showed that the physical properties of PDBEs are suitable for long-range transport in air, and other studies have shown that long-range atmospheric transport is likely (Hale et al., 2003; Hale et al., 2006). HBCDs Table 7.13 summarises the results for Sum HBCD in air from both stations. There was little difference between the mean values at Birkenes and Zeppelin in 2006, whereas the mean level at Birkenes was considerably lower in the 2007 data set. The maximum and minimum concentrations at the two stations were almost identical. HBCDs have a long enough atmospheric lifetime to undergo long-range transport away from point sources of production and use (Law et al., 2006). Their distribution patterns in the environment would therefore be expected to be similar to those of other semi-volatile POPs such as PCBs and PCDD/ PCDF. Figure 7.6 and Figure 7.7 show the concentrations of Sum HBCD in all individual samples from both stations. The dominant isomer in Sum HBCD is γ- 44

46 HBCD, which accounted for 71% and 72% of the total at the two stations. The main component of technical HBCD is γ-hbcd. This is also the main component in sediments, whereas α-hbcd is usually dominant in biota (Birnbaum and Staskal, 2004). However, the analytical process itself can affect the composition of HBCD, since changes in isomeric profile can occur at temperatures above 160 C (GC injectors are usually hotter than this). Another element of uncertainty that affects the isomeric profile is that the sample preparation method used here has proved to result in a negative bias for β-hbcd (i.e. its loss). After this was discovered, the method was corrected and studies are being conducted to estimate the size of the loss. Table Key results for Sum HBCD in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements Mean 2006: 7.56 and 7.03 pg/m Figure 7.6. Sum HBCD in all samples at Birkenes [pg/m 3 ]. 45

47 Figure 7.7. Sum HBCD in all samples at Zeppelin [pg/m 3 ]. Table 7.14 shows some results of measurements of HBCDs in air at stations in Sweden, both near presumed sources (towns) and at background stations, compared with those of the present study. The levels found in the present study are of the same order of magnitude as those from the Swedish background stations. Some of the Swedish measurements were made close to point sources, and the concentrations are therefore much higher. Table Measurements of Sum HBCD in air [pg/m 3 ]. Measurement station/site HBCD concentration [pg/m 3 ] Reference Stockholm, schoolyard 78 Remberger et al Stockholm, street 610 Remberger et al m fra textile factory, Borås 740 Remberger et al XPC* factory, Sweden (10m from outlet of ventilation system) Remberger et al Aspvreten, south of Stockholm 25 Remberger et al Rørvik, Swedish west coast 5 Remberger et al Ammarnäs, Lappland 6.1 Bergander et al Hoburgen, Gotland 5.3 Bergander et al Pallas, N. Finland 3 Remberger et al Birkenes 4.15 Zeppelin 6.54 * Extruded polystyrene 7.2 Polyfluorinated substances Several hypotheses have been advanced to explain how PFAS are transported from densely populated areas to background areas. One of these (Ellis, 2004) is based on the idea that PFOS and perfluorinated carboxylic acids (PFCAs) are degradation products of neutral 46

48 PFAS. These precursors are more volatile (Lei, 2004) than PFOS/PFCAs, and will more easily undergo long-range atmospheric transport to background areas where degradation takes place. Possible precursors of PFCAs and PFOS are fluorotelomer alcohols (FTOHs) (Ellis, 2004) and fluorooctane sulfonamides and sulfonamidoethanols (FOSAs/FOSEs) (Martin, 2006; D'eon, 2006). It has also been proposed that fluorotelomer olefins (FTtolefins) may degrade to form PFCAs (Prevedouros, 2006). Another hypothesis from the same author is that direct transport of PFAS with ocean currents is far more important than atmospheric transport, while a third is that PFAS from seawater can be transferred to the atmosphere through the formation of marine aerosols and then be transported in particle-bound form in the atmosphere. Simcik (2005) has proposed that PFOS and PFCAs may be emitted from primary sources adsorbed on particulate matter and be transported to remote areas with the air masses. Barton et al. (2006) studied the distribution of PFOA on particulate matter near a manufacturing plant for perfluoropolymers, and found that most of the PFOA was present in the form of the finest grade of airborne particulate matter. A study of the concentrations of FTOHs and sulfonamides in the North American troposphere (found to be pg/m 3 and pg/m 3 respectively) indicates that the spatial distribution of these substances is inhomogeneous, perhaps because point sources are important. Ellis et al. (2003) concluded that the atmospheric lifetime of FTOHs is about 20 days, irrespective of the number of fluorinated carbon atoms in the straight chain of the molecule. This means that FTOHs can be transported to areas remote from the source. An air parcel moving at a speed of 4m/s (14 km/h) will travel 7000 km in the course of 20 days, and it is therefore possible for FTOHs from a point source to be carried to remote areas. PFOA PFOA is a surfactant that is widely used in the production of chemicals. It is emitted directly to the atmosphere during the manufacture of fluoropolymers (Barton et al., 2006). It is classified as toxic and carcinogenic (Posner et al., 2007). Table 7.15 lists some atmospheric measurements of PFOA. Table Atmospheric measurements of PFOA. Reference Site pg/m 3 Barber et al. Indoor air, Tromsø 4.4 Barber et al. Kjeller 1.54 Barber et al. Hazelrigg * 101 Barber et al. Manchester 15.7 Barber et al. Mace Head 8.9 Jahnke et al English Channel 1.75 Jahnke et al Bay of Biscay 1.0 Jahnke et al West of Gibraltar 0.5 Jahnke et al West of Western Sahara 0.6 Jahnke et al West of Guinea 0.7 Jahnke et al South of Côte d'ivoire 0.3 Birkenes 1.04 Zeppelin

49 Barber et al. (2007) measured concentrations of PFOA at sites in Manchester, Hazelrigg (northwestern England, close to the coast), Mace Head (west coast of Ireland), Kjeller (near Oslo) and four indoor locations in Tromsø (north Norway). All the concentrations were higher than that found at Zeppelin, while the figure for Kjeller was of the same order of magnitude as at Birkenes. Jahnke et al. (2007b) measured PFOA concentrations in air during a cruise from Bremerhaven to Cape Town (Table 7.15). The highest value they found (1.75 pg/m 3 ) was in a sample taken while sailing through the English Channel. From then on, they found lower and lower values as they sailed southwards west of Africa. In the Bay of Biscay, the concentration was almost identical to that measured at Birkenes. The lowest level measured before concentrations dropped below the detection limit was in air sampled south of Côte d'ivoire, where there were no local pollution sources, and was very close to the mean value at Zeppelin. Table Key results for PFOA in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements PFOS Perfluorooctyl sulfonate is considered to be one of the most important polyfluorinated substances because it has been produced industrially in large quantities and because of its wide global distribution. Production has been dropping steeply as its use is phased out, and current production figures are unknown (Herzke et al., 2007). Several PFAS compounds can degrade to form PFOS, which is very stable in the environment and is classified as persistent, toxic and bioaccumulative. Because of the low volatility of PFOS (vapour pressure at 20 C: 3.31x10-4 Pa (Herzke et al., 2007)), the atmosphere is unlikely to be an important sink, but its tendency to become adsorbed to particulate matter can result in elevated concentrations in the particulate phase. Table 7.17 summarises the results for PFOS. The mean concentration at Birkenes is about 1.8 times higher than at Zeppelin. Table 7.17.Key results for PFOS in air [pg/m 3 ]. Birkenes Zeppelin Mean Range No. No. Mean Range measurements measurements Mean 2006: 0.77 and 0.11 pg/m 3. The results reported by Barber et al. (2007) for PFOS in air at the three stations Kjeller, Hazelrigg and Manchester were 1.0, 1.6 and 7.1 pg/m 3 respectively. The concentration at Birkenes was somewhat lower than the mean value at Kjeller and lower than the levels at the two other stations. The maximum value at Zeppelin was about half the concentration found at Kjeller and lower than those for Hazelrigg and Manchester. Martin et al. (2002) found that the concentration in indoor air was about 100 times the level measured in outdoor air. Indoor air may therefore be a source of PFOS in outdoor air. 48

50 Jahnke et al. (2007b) measured PFOS concentrations in air during a cruise from Bremerhaven to Cape Town. The minimum and maximum values they found are compared with the values from Birkenes and Zeppelin in Table Table Measurements of PFOS from Birkenes and Zeppelin, and data from Jahnke et al. (2007b). Minimum Maximum Bremerhaven-Cape Town Birkenes Zeppelin The highest value was measured in the first sample taken after the ship left Bremerhaven, and was markedly higher than the maximum values from the present study, while the minimum value was of the same order as the minimum values found in the present study. The lowest values were found in samples taken well west of Angola and Namibia, i.e. in air that was not influenced by local pollution sources. 49

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52 Führer, U. and Ballschmiter, K. (1998) Bromochloromethoxybenzenes in the marine troposphere of the Atlantic Ocean: A group of organohalogens with mixed biogenic and anthropogenic origin. Environ. Sci. Technol., 32, Gouin, T., Thomas, G.O., Chaemfa, C., Harner, T., Macay, D. and Jones, K.C. (2006) Concentrations of decabromdiphenyl ether in air from Southern Ontario: Implications for particle-bound transport. Chemosphere, 64, Hale, R.C., Alaee, M., Manchester-Neesvig, J.B., Stapleton, H.M. and Ikonomou, M.G. (2003) Polybrominated diphenyl ether flame retardants in the North American environment. Environ. Internat., 29, Hale, R.C., La Guardia, M.J., Harvey, E., Gayor, M.O. and Mainor, T.M. (2002) Potential role of fire retandant-treated polyurethane foam as a source of brominated diphenyl ethers to the US environment. Chemosphere, 46, Hale, R.C., La Guardia, M.J., Harvey, E., Gayor, M.O. and Mainor, T.M. (2006) Brominated flame retardant concentrations and trends in abiotic media. Chemosphere, 64, Herzke, D., Schlabach, M., Mariussen, E., Uggerud, H., Heimstad, E. (2007) A litterature survey on selected chemical compounds. Oslo, Statens forurensningstilsyn (Statlig program for forurensningsovervåking) (TA-2238/2007). Jahnke, A., Ahrens, L., Ebinghaus, R. and Temme, C. (2007a) Urban versus remote air concentrations of fluorotelomer alcohols and other polyfluorinated alkyl substances in Germany. Environ. Sci. Technol., 41, Jahnke, A., Ahrens, L., Ebinghaus, R., Berger, U., Barber, J.L. and Temme, C. (2007b) An improved method for the analysis of volatile polyfluorinated alkyl substances in environmental air samples. Anal. Bioanal. Chem., 387, Jahnke, A., Huber, S., Temme, C., Kylin, H. and Berger, U. (2007c) Development and application of a simplified sampling method for volatile polyfluorinated alkyl substances in indoor and environmental air. J. Chromatogr. A, 1164, 1-9. Kaiser, M.A., Larsen, B.S., Kao, C.P.C. and Buck, R.C. (2005) Vapor pressures of perfluorooctanoic,- nonanoic, -decanoic, -undecanoic, -dodecanoic acids. J. Chem. Eng. Data, 50, Law, R.J., Allchin, C.R., de Boer, J., Covaci, A., Herzke, D., Lepom, P., Morris, S., Tronczynski, J. and de Wit, C.A. (2006) Levels and trends of brominated flame retardants in the European environment. Chemosphere, 64, Lei, Y.D., Wania, F., Mathers, D. and Mabury, S.A. (2004) Determination of vapor pressures, octanol-air, and water-air partition coefficients for polyfluorinated sulfonamide, sulfonamido-ethanols, and telomer alcohols. J. Chem. Eng. Data, 49, Manø, S., Herzke, D. og Schlabach, M. (2008) Nye miljøgifter i luft. Kjeller (Statlig program for forurensningsovervåkning. Rapport 1023/2008) (TA-2408/2008). (NILU OR 16/2008). 51

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54 Appendix A Raw data 53

55 54

56 TBA, PBB and PBDE Birkenes TBA BB_15 BB_153 BDE_28 BDE_47 BDE_49+71 BDE_66 BDE_77 BDE_85 BDE_99 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m <0.01 < i <0.01 < <0.01 < < g <0.01 < < <0.01 < <0.01 < g <0.01 < <0.01 < g <0.01 < <0.01 < <0.01 < <0.01 < g <0.01 < <0.01 <0.01 < < < <0.01 < <0.01 <0.01 <0.01 < < <0.01 < g < <0.01 <0.01 < < <0.01 < <0.01 < <0.01 < <0.01 < <0.01 < <0.01 < <0.01 <0.01 < <0.01 < <0.01 < Field blank i <0.01 < Birkenes BDE_100 BDE_119 BDE_138 BDE_153 BDE_154 BDE_183 BDE_196 BDE_206 BDE_209 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m <0.01 < i.g i <0.01 < g < <0.01 < g i <0.14 < <0.01 < g 0.02 <0.01 <0.02 < < g 0.02 <0.01 <0.02 < <0.01 < g < <0.01 < g g < <0.01 <0.03 < < g < g <0.01 < g < g g <0.01 < g g g <0.01 <0.02 < g < g < g g <0.01 < < <0.01 < g < <0.01 < < i <0.01 < i 0.02i < i 5.50 Field blank 0.19 <0.01 < <0.01 <

57 Zeppelin TBA BB_15 BB_153 BDE_28 BDE_47 BDE_49+71 BDE_66 BDE_77 BDE_85 BDE_99 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m <0.01 < i <0.01 < g <0.01 < <0.01 < <0.01 < < g <0.01 < < <0.01 < <0.01 < <0.01 < <0.01 < < i g <0.01 < <0.01 <0.01 < <0.01 < <0.01 < <0.01 < i i <0.01 < g <0.01 < <0.01 <0.01 < <0.01 < <0.01 < <0.01 < < g <0.01 < i <0.010 < i <0.01 < i < <0.01 < < i <0.01 < <0.01 <0.01 < Field blank 0.12 <0.01 <0.01 < <0.01 <0.01 <0.01 <0.01 <0.06 i: Interference g: Low recovery of internal standard Zeppelin BDE_100 BDE_119 BDE_138 BDE_153 BDE_154 BDE_183 BDE_196 BDE_206 BDE_209 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m <0.01 < i i <0.01 < <0.01 < <0.01 < g < <0.01 < g < <0.01 <0.02 <0.01 <0.01 < <0.01 <0.01 <0.01 < g < g <0.01 < g 0.29g 0.08g < g 4.22g <0.01 <0.01 <0.01 <0.01 <0.01 < <0.01 <0.01 <0.01 < g < <0.01 < i 0.02g 0.04i g <0.01 <0.01 <0.01 <0.01 < <0.01 <0.02 <0.01 <0.01 <0.01 <0.04 < <0.01 < g 0.01i 0.05i <0.01 < i 0.03i 0.11i <0.01 < i 0.02i 0.01g i <0.01 < <0.01 < g <0.01 < <0.01 <0.01 < Field blank <0.02 <0.01 <0.01 <0.01 <0.01 < i: Interference g: Low recovery of internal standard 56

58 HBCD Birkenes α-hbcd β-hbcd γ-hbcd Zeppelin α-hbcd β-hbcd γ-hbcd pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m < < < i 0.18i i < g < <0.26 < < < < < < < <0.25 < i < < < <0.15 < < <0.08 < < < < < < < < i i 0.07i Field blank 0.49 < <0.11g <0.07 <0.17 i: Interference Field blank 0.25 < Birkenes 6:2 PFOSA PFBS PFHxS PFOS PFDcS PFBA PFHxA PFHpA PFOA PFNA PFDcA PFUnA FTS pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m <0.54 <0.07 <0.07 < < <0.30 < <0.24 <0.29 < <0.46 <0.06 <0.06 < < <0.59 < <0.55 <0.44 < <1.15 <0.12 <0.10 < < <0.44 < <0.51 <0.38 < <0.84 < <0.06 <0.06 < <0.38 < <0.43 <0.36 < <0.38 <0.05 <0.06 < < <0.23 <0.21 <0.27 <0.20 <0.24 < <0.84 < <0.06 <0.06 < <0.38 < <0.43 <0.36 < <2.0 <0.20 <0.27 <0.12 <0.10 < <0.64 <0.61 <0.59 <0.56 < <0.67 <0.07 <0.05 < < <0.44 < <0.47 <0.55 < <1.67 <0.22 <0.14 < <0.07 <0.25 <0.68 <0.58 <0.76 <0.79 <0.53 < <0.04 <0.04 < < <0.18 <0.18 <0.16 <0.27 <0.22 < <0.20 <0.02 <0.08 < < <0.18 <0.23 <0.13 <0.24 <0.26 < <0.85 <0.08 <0.06 < < <0.41 <0.41 <0.44 <0.52 <0.45 < <0.64 <0.06 <0.04 < <0.39 <0.32 <0.29 <0.38 <0.34 < <0.71 <0.07 <0.06 < < <0.44 < <0.51 < <0.73 <0.06 <0.06 < < <0.40 < <0.53 <1.23 < <0.65 <0.08 <0.06 < < <0.40 < <0.49 <0.41 <0.37 Field <0.34 <0.03 <0.03 < <0.01 <0.12 <0.18 <0.15 <0.16 <0.22 <0.42 <0.19 blank 57

59 Zeppelin 6:2 PFOSA PFBS PFHxS PFOS PFDcS PFBA PFHxA PFHpA PFOA PFNA PFDcA PFUnA FTS pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m 3 pg/m <0.42 <0.04 <0.04 < < < <0.20 < <0.17 <0.02 <0.03 < < <0.11 < <0.19 <0.19 < <0.14 <0.02 <0.02 < < <0.13 < <0.20 <0.19 < <0.19 <0.02 <0.02 < < <0.14 < <0.24 <0.28 < <0.50 <0.06 <0.06 < g < g <0.44 < g <0.57 <0.50 < <0.16 <0.02 <0.03 < < <0.15 < <0.41 <0.30 < <0.16 <0.02 < < <0.10 < <0.15 < <0.44 <0.03 <0.04 < < <0.13 < <0.29 < <0.20 <0.02 <0.08 < < <0.18 < < < < <0.11 < < <0.83 <0.01 <0.24 < < <0.10 < <0.15 <0.36 < <0.97 <0.04 <0.06 < <0.21 <0.08 <0.32 < <0.24 <0.31 <0.14 Field <0.01 <0.01 <0.01 < <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 blank g: Low recovery of internal standard 58

60 Climate and Pollution Agency, P.O. Box 8100 Dep, N-0032 Oslo Street address: Strømsveien 96 Tel: Fax: postmottak@klif.no Internet: Carried out by: Norwegian Institute for Air Research (NILU) SPFO 1077/2010 Project manager: Stein Manø, NILU Contact Climate and Pollution Agency: Tor Johannessen TA number: 2689/2010 Authors: Stein Manø, Dorte Herzke, Martin Schlabach Year: 2010 No of pages: 60 Climate and Pollution Agency s contract number: Published by Norwegian Institute for Air Research Project funded by Climate and Pollution Agency NILU project number: O NILU report number: OR 28/2008 Title Norwegian and English: Nye miljøgifter i luft 2007 New organic pollutants in air, 2007 Sammendrag summary: Denne undersøkelsen rapporterer konsentrasjonsnivåer av de nye organiske miljøgiftene bromerte flammehemmere og polyfluorerte alkylstoffer i luft på bakgrunnsmålestasjonene Birkenes og Zeppelinfjell, Ny-Ålesund. This study reports concentration levels of new organic pollutants (brominated flame retardants and polyfluorinated substances) in air at the background stations Birkenes (southern Norway) and Zeppelin (Svalbard). 4 emneord: BFH PFAS Bakgrunnskonsentrasjoner Luft 4 key words: Brominated flame retardants PFAS Background concentrations Air