Marko Filipovic. A review of contamination of surface-, ground-, and drinking water in Sweden by perfluoroalkyl and polyfluoroalkyl substances (PFAS)

Transcription

1 A review of contamination of surface-, ground-, and drinking water in Sweden by perfluoroalkyl and polyfluoroalkyl substances (PFAS) Marko Filipovic ATV Jord og Grundvand møde 10 oktober om PFAS

2 Outline Historical background. PFAS in products and sources of PFAS in Sweden. Results: PFAS in groundwater, surface water and drinking water. Future challenges. NIRAS PFAS management. Summary. Figure: The Fate of the good deed. (Andreas Ekoutsidis ). 2

3 Use of firefighting foam and PFAS impact of Swedish airfields Marko Filipovic, NIRAS- ATV Jord og Grundvand møde 10 oktober om PFAS 1995 a b Reports from the Swedish Rescue Services Agency where the problem with firefighting is noted. Foam effect on the environment, Report P / Foam and oil emulsion's toxicity and foaming effect on oil separator, Report R / c PFOS is found in high concentrations in Rosersbergsviken, Mälaren. The ground and surface water is affected by leakage of PFAS from Rosersberg Fire fighting training site. (Homström and Järnberg) NIRAS 2009 d The research project RE-PATH is initiated by the Swedish Environmental Protection Agency, via the IVL Foundation, and Swedavia. With goal to map the spread/and effects of PFAS leakage from Arlanda Airport and Göteborg Landvetter Airport e PFOS is detected at Malmö Airport in connection to the collection system at the fire training site. NIRAS 2009 f High levels of PFAS are detected at F14 Halmstad gh Filipovic et al NIRAS During a summer school organized by ITM at Stockholm University. High levels of PFAS are detected in potable water in Tullinge (F 18). Tullinge Waterworks closes its drinking water production. The pollution situation of PFAS in Tullinge (eg, F 18) is investigated by WSP i Filipovic et al. NIRAS High levels of PFAS are detected in Uppsala water, which leads to the closure of water k High levels of PFAS are detected in Kallax 2013 j High levels of PFAS are detected in Kallinge l DuPont starts producing PTFE n Taves and others suggest that PFOA is present in blood m Commercial production of PFAS products starts at 3M o PFOA is detected in blood from workers at 3M M initiates a phase-out of PFOS p PFOA is detected for the first time in drinking water, Washington USA. (Homström and Järnberg) NIRAS 2001 The Swedish Environmental Protection Agency performs the first screening assignment of PFAS in: air sediment, sedimenterande material surface water outflow waste water treatment plants leachate from landfills air 2003 SGU performs on behalf of the Swedish Environmental Protection Agency, a measurement of PFAS in groundwater at national environmental monitoring stations Nordic screening study of PFOS: rainwater sediment sludge M phases out its PFOA based chemistry PFOS is incorporated into the Stockholm Convention on Persistent Organic Pollutants (POP) IVL / NILU commissioned by the Swedish Environmental Protection Agency 2005 The results were presented in a report in November 2006 (Results from the Swedish National Screening Program 2005). Milestones in PFAS research and regulation focusing on Sweden 2011 EU suggests (Environmental quality standard EQS) för PFOS in water and biota The Swedish Armed Forces decides to prohibit the use of PFOS, information sent to Armed Forces on the entry into force of the prohibition Report from KEMI PFAS in AFFF Report from Svensk Vatten, about PFAS in potable water National food agancy, Swedem puts guideline values for 7PFAS in potable water to 90 ng/l SGI sets advisory/guidance values for PFOS in groundwater and soil National food agancy, Swedem puts guideline values for 11 PFAS in potable water to 90 ng/l

4 Use of firefighting foam and PFAS impact of Swedish airfields Marko Filipovic, NIRAS- ATV Jord og Grundvand møde 10 oktober om PFAS 1995 a b Reports from the Swedish Rescue Services Agency where the problem with firefighting is noted. Foam effect on the environment, Report P / Foam and oil emulsion's toxicity and foaming effect on oil separator, Report R / c PFOS is found in high concentrations in Rosersbergsviken, Mälaren. The ground and surface water is affected by leakage of PFAS from Rosersberg Fire fighting training site. (Homström and Järnberg) NIRAS 2009 d The research project RE-PATH is initiated by the Swedish Environmental Protection Agency, via the IVL Foundation, and Swedavia. With goal to map the spread/and effects of PFAS leakage from Arlanda Airport and Göteborg Landvetter Airport e PFOS is detected at Malmö Airport in connection to the collection system at the fire training site. NIRAS 2009 f High levels of PFAS are detected at F14 Halmstad gh Filipovic et al NIRAS During a summer school organized by ITM at Stockholm University. High levels of PFAS are detected in potable water in Tullinge (F 18). Tullinge Waterworks closes its drinking water production. The pollution situation of PFAS in Tullinge (eg, F 18) is investigated by WSP i Filipovic et al. NIRAS High levels of PFAS are detected in Uppsala water, which leads to the closure of water k High levels of PFAS are detected in Kallax 2013 j High levels of PFAS are detected in Kallinge l DuPont starts producing PTFE n Taves and others suggest that PFOA is present in blood m Commercial production of PFAS products starts at 3M o PFOA is detected in blood from workers at 3M PFAS-7 in ground water and drinking water are available. 3M initiates a phase-out of PFAS PFOS. 3M phases out its PFOA based chemistry p PFOA is detected for the first time in drinking water, Washington USA. 13 Years collection of data before guideline values for PFOS and (Homström and Järnberg) NIRAS 2001 The Swedish Environmental Protection Agency performs the first screening assignment of PFAS in: air sediment, sedimenterande material surface water outflow waste water treatment plants leachate from landfills air 2003 SGU performs on behalf of the Swedish Environmental Protection Agency, a measurement of PFAS in groundwater at national environmental monitoring stations Nordic screening study of PFOS: rainwater sediment sludge 2009 PFOS is incorporated into the Stockholm Convention on Persistent Organic Pollutants (POP) IVL / NILU commissioned by the Swedish Environmental Protection Agency 2005 The results were presented in a report in November 2006 (Results from the Swedish National Screening Program 2005). Milestones in PFAS research and regulation focusing on Sweden 2011 EU suggests (Environmental quality standard EQS) för PFOS in water and biota The Swedish Armed Forces decides to prohibit the use of PFOS, information sent to Armed Forces on the entry into force of the prohibition Report from KEMI PFAS in AFFF Report from Svensk Vatten, about PFAS in potable water National food agancy, Swedem puts guideline values for 7PFAS in potable water to 90 ng/l SGI sets advisory/guidance values for PFOS in groundwater and soil National food agancy, Swedem puts guideline values for 11 PFAS in potable water to 90 ng/l

5 Advances in characterization of per- and poly-fluorinated alkyl substances (PFAS). Conventional analysis of PFAS with HPLC-MS/MS has expanded from PFOA and PFOS to more than >20 different PFAS including linear/branched homologues. High resolution mass spectrometry has been applied with great success and more than 40 different subgroups of PFAS have been detected. Advances in analysis of short chained PFAS. TOP-assay oxidation of PFAA-precursors to measurable PFAAs. Combustion ion chromatography (CIC) and Particle induced gamma ray emission (PIGE) have been used to asses total organic fluorine (TOF). PFAS homologues are not measured! Results are obtained as fluorine ions (F) which can be converted to PFAS equivalents. 5

6 Advances in characterization of per- and poly-fluorinated alkyl substances (PFAS). Conventional analysis of PFAS with HPLC-MS/MS has expanded from PFOA and PFOS to more than >20 different PFAS including linear/branched homologues. NIRAS is one of the first consultant High resolution mass spectrometry has been applied with great success and more than 40 different subgroups of PFAS have been detected. companies in EU to apply methods such as Advances in analysis of short chained PFAS. TOP-assay and TOF (AOF) in full scale TOP-assay oxidation of PFAA-precursors to measurable PFAAs. environmental investigational studies with Combustion ion chromatography (CIC) and Particle induced gamma ray emission (PIGE) have been used to asses total organic fluorine (TOF). PFAS homologues are not measured! Results are obtained as fluorine ions (F) which can be converted to PFAS equivalents. great success. 6

7 Applications of PFAS in various industries Applications of PFAS Textile And Leather Industry Impregnation of paper Additative in paints Industrial chrome plating Hydraulic fluids in the aviation industry Aqueous film forming foam (AFFF) Consumer products -Cosmetics -Electronics 7 IVL 2016

8 The presence of PFAS in garment Greenpeace 8 Greenpeace

9 Leakage of PFAS from garment Schellenberger

10 Measurable PFAS vs AOF in consumer products 10

11 PFAS in Aqueous film forming foams 11

12 PFAS in Aqueous film forming foams Prior TOP-assay Post TOP-assay 12

13 Summary: measurable PFAS in products Consumer and industrial products sold on the Nordic market, contain PFAAs, FTOHs and a significant amount of other PFAS. PFAS will be disposed from the garment and consumer products during their life-cycles (landfills) to the environment groundwater surfacewater. A notable amount of the PFAS present are not included in the PFAS measured by conventional HPLC-MS/MS. PFOA and PFOS are regulated however, new PFASs are entering the market! TOP-assay can provide a better picture of the presence of PFAS substances (which are not measured with current analytical tools) in both historical and new fire fighting foams. New analytical methods such as absorbable organic fluorine (AOF) can provide a better picture of the presence of PFAS substances (as we do not measure today) in different matrices. 13

14 Identified potential PFAS sources in Sweden Rapport 6709 Mars 2016 >2000 sources Including: Industries Landfills Firefighting training sites 14

15 PFAS sources-firefighting training sites Rapport 6709 Mars 2016 Rapport 6709 Mars firefighting training sites in connection with military and civilian airports have been identified in the geographical survey. According to the survey, 323 fire training sites are in operation or dismissed in Sweden. Investigations performed by NIRAS in Sweden encompassing various sectors such as: fire training sites, industries and private sector. 15

16 Log Concentration [ng/l] PFAS in surface water in Sweden Measurement of PFAS 26 and PFOS (ng/l) in surface water Average concentration of PFOS in surface water Rapport 6709 Mars 2016 Rapport 6709 Mars 2016 Measurement of PFAS 26 and PFOS (ng/l) content in 215 surface water samples included in the Water Framework Directive (screening 2015). The height of the blue stack is sum concentrations of PFAS-26, yellow-colored stack indicates the level of PFOS. Orange vertical line indicates EU EQS for PFOS, 0.65 ng/l. Note that the scale is logarithmic. Geographic distribution of PFOS concentrations in surface water. Dots with orange and red color illustrate concentrations above European EQS for PFOS, 0.65 ng/l. 16

17 Case study: PFAS in surface water in Lake Mälaren (Stockholm) Lake Mälaren provides drinking water for approximately 2 million people. PFAA concentrations in water exceeded >20 ng/l in Lake Mälaren. Linear and branched PFAS were analyzed. T O P Post TOP-assay results show that PFAS concentrations increse with 57%. PFAA-precursor of shorter chain PFAS are present in Lake Mälaren, posing a risk to humans and biota. Stockholm 17

18 Log Concentration [ng/l] PFAS in groundwater in Sweden Measurement of PFAS 26 and PFOS (ng/l) in surface water Rapport 6709 Mars 2016 Average concentration of PFOS in ground water Rapport 6709 Mars 2016 Measurement of PFAS 26 and PFAS 7 (ng/l) in N=173 samples from water supplies. The height of the blue stack is sum concentrations of PFAS-26, yellow-colored part indicates the level of PFOS. Orange line indicates the National food agancy, Swedem guideline values f or PFAS 7 90 ng/l. Note that the scale is logarithmic. 18 Geographic distribution of PFOS concentrations in groundwater. Dots with orange and red color illustrate concentrations above European EQS for PFOS, 0.65 ng/l.

19 Frequency [%] Frequency [%] PFAS in raw and drinking water in Sweden Raw water Drinking water Rapport 6709 Mars 2016 Rapport 6709 Mars 2016 Log Concentration [ng/l] Reverse cumulative distribution of sum concentrations of PFAS-7 in raw water used for drinking water production in waterworks (N = 1283). The blue line marks the action limit 90 ng/l and the orange line shows the 900 ng/l action limit for sum PFAS samples (about 16%) have concentrations above or equal to 90 ng/l and 6 samples (about 0.5%) has a concentration above or equal to 900 ng/l. Log Concentration [ng/l] Reverse cumulative distribution of sum concentrations of PFAS-7 in drinking water from waterworks (N = 298). The blue line marks the action limit 90 ng/l and the orange line shows action limit 900 ng/l for PFAS samples (about 5%) have a concentration above or equal with 90 ng/l and 3 samples (approximately 1%) have a concentration above or equal to 900 ng/l. 19

20 Summary: PFAS in Swedish water In Sweden there are more than 2000 potential sources, 28 firefighting training sites close by airports and >300 municipal firefighting training sites. Highest PFAS concentrations in surface water are found nearby identified point sources. PFAS concentrations in all surface waters are not above EU EQS for PFOS 0.65 ng/l. TOP-assay revealed presence of PFAA-precursors of shorter chain PFAAs in Lake Mälaren. Great amount of focus have been applied on PFAAs in ground and drinking water. However, there is a lack of information regarding presence of PFAA-precursors! 20

21 Future challenges Current technologies are only being able to catch a selected number of PFAS. New methods such as TOP-assay and TOF (AOF) should be used in future monitoring programs, better data=better risk assessments. The current screening has given a first overview of measurable PFAS in surface and ground water. However, the presence of potentially harmful PFAAprecursors might be much higher. There are large groundwater monitoring gaps in Sweden (Destouni et al. 2008; Baresel and Destouni 2009). Approximately ~ private drinking water wells which provide for 1.2 million people have to be monitored as they lack any protection and control. The PFAS group is enormous (more than 3000 different substances may have been in use, Naturvårdsverket (2016)) and when authorities ban one, producers change to another closely related substance with properties like the first one (Gomis et al. 2015). 21

22 NIRAS PFAS Managment NIRAS is involved in employing novel analytical techniques and is involved in development of new technologies together with academia for monitoring, remediation and treatment of PFAS in unsaturated and saturated zone: NIRAS is working together with commercial laboratories and academia to push forward the development for better PFAS analysis. Experienced employer of GAC-filters (Gardemoen airport Oslo). NIRAS is working on cost effective and widely aviable sorbent materials which remove both short and long chain PFAS. NIRAS is currently working on a TUFFO-project (SGI), PFAS-stop together with SLU and Uppsala University. 22

23 Summary In Sweden, PFAS research has been conducted since the early 2000s. The guideline values for PFOS in ground water and sum PFAS-7(PFAS-11) in drinking water have been available since in late PFAS in consumer products, industrial products and fire fighting foam will during their life cycle leak to the environment where they pose a risk to ground and surface water contamination. There are many possible and confirmed sources of PFAS >2000 in Sweden. There are major shortcomings in today's monitoring of total amount of PFAS present in the surface/ ground water because only the PFAS that can be measured are taken into account. Novel methods such as TOP assay and TOF (AOF) can be used in combination conventional HPLC-MS/MS to illustrate the amount of PFAA precursors, leading to better results and better risk assessments. 23

24 Thank you for your attention Highly appritiated scientific review. o >3000 downloads Contact Marko Filipovic PhD marko.filipovic@niras.se Katrin Holmström PhD katrin.homstrom@niras.se Sara Holmström PhD Sara.holmström@niras.se Johan Edvinsson Johan.edvinsson@niras.se Ulrika Iverfelt Ulrika.iverfelt@niras.se 24