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Pdf 22.01.2016 86 Weberr PFOS-PFAS Roland Weber/Dirk Roland Weber*, Dirk Skutlarek**, Harald Färber**, Paul Kröfges*** Claudia Baitinger***, Ingo Gödeke*** *POPs Environmental Consulting, Göppingen, Germany **University Bonn, Institute for Hygiene and Public Health, Bonn, Germany ***BUND (FoE Germany) Nordrheinwestfalen e.V., Düsseldorf, Germany http://www.dioxin20xx.org/pdfs/2007/07-634.pdf ¾ Screening of PFOS, PFOA and other PFAS in the Rhine river and tributaries (Skutlarek, Färber, Exner, Univ. Bonn, March 2006) ¾ High PFAS-contamination in Rhein tributary rivers Ruhr, Emscher and Lippe (near the city of Essen). 1 Tracing the PFAS- contamination in the Ruhr back to Möhne river and tributary creeks. Extreme high concentrations of PFOA and other PFAS in the Moehne river and tributaries. Skutlarek, Exner, Färber, Environ Sci Pollut Res 13 (5) 299 – 307 (2006) 2 Contam Sites Ruhrwasser (Presentation 12/2006) Lake Moehne (drinking water reservoir for ca. 5 million people) with a volume of 134.5 million m3, was contaminated with ΣPFAS of 822 ng/l. Calculated concentration in the lake: 110.5 kg PFAS. ¾After July 2006: use of two other dams with non contaminated water to dilute high concentrations of theMoehnedam to adjustthe concentration in the Ruhr to below 300 ng PFAS/l (just meeting the preliminarily established drinking water limits). ¾ The Moehne Reservoir released slowly the approx. 110 kg PFAS into the Ruhr and via Rhein finally into the North Sea contaminating on their way drinking water and fish. 3 ¾ The PFOS/PFOA contaminated agricultural fields resulted from mismanagement of PFAS contaminated sludge of a PFAS producer which was imported via a Dutch trader to a German company (in accordance with EU hazardous Waste Shipment Regulation (EEC 259/93). ¾ In a criminal act the German company (GW Umwelt) then labelled the sludge as “bio-solids” and gave it to farmers. In September 2006 the BUND (FoE Germany) accused the company and also the local authority Soest. ¾ After the contamination was revealed the company proclaimed bankruptcy and the former owner and CEO of the company went to court. Court investigation ongoing. Surface Water Drinking Water ¾Similar contamination ¾Drinking Water max at 700ng/l PFAS ¾Several large cities (Dortmund, Essen) above 100 ng/l and temporarily above 300 ng/l Investment of 100 million Euro in water works in the region ! 4 Local/State governments approached German Health Agency for clarification and help (05/2006). ¾ No drinking water guideline worldwide for PFC. ¾ No comprehensive Risk Assessment that would have allowed a straight forward decission for limits (after 50 years high volume production of PFOS/PFOA used in daily life/household!!!). ¾ German Health Agency made a preliminary recommendation for drinking water limits PFAS. (21.06.2006) Type of Limits Abrev. PFOS+PFOA Reasoning Target value GOW ≤ 0.1 µg/l Health precaution (minimum quality) (Life span) Health guiding LW ≤0.3 µg/l Acceptable value value (Life span) Precautionary VMWS 0.5 µg/l Precuationary action value infants protection infants Action value adults MW = 5.0 µg/l Recom: Not use for VMW0 nutrition purpose Stellungsnahme Trinkwasserkommission BMG (beim UBA) 21.06.06; revised 13.07.06 Risk assessment New Yersey state (2007): Limit drinking water PFOA* 40 ng/l. 5 (Ca. 500ng/l in drinking water for ca. 3 years) Children Man Woman University Bochum/Erlangen-Nürnberg, LUA NRW Study on human PS contam. in areas with elevated PS drinking water conaminatiion. 3/2007 450 PFOA PFOS PFHxS PFBS 400 (Ca. 500 ng/l in drinking water for ca. 3 yeas) 350 Diabetis 300 Insipitus 250 Children (and mother) 200 150 100 50 PFCs in blood plasma (ug/l) plasma blood PFCs in 0 Child 1 Child 2 Mother Men 1 Men 2 University Bochum/Erlangen-Nürnberg, LUA NRW Study on human PS contam. in areas with elevated PS drinking water conaminatiion. 05/2007 6 Remediation Still ca. + 50 ng PFCs Contam. Site >100 ng/l + 100 ng/l > 37 industrial sources & Sewage treatment facility + 50 ng/l Other contam. Sites ¾ Approximately 250,000 tons of imported sludge were distributed as “Soil Improver“ on approx. 1300 sites in Germany including agricultural land, grazing fields and forests. Luckily only a minor part contained high levels of PFAS (what did the other sludge include?). ¾ Start of national monitoring activities for PFOS/PFOA contamination in German rivers and water works. ¾ In course of this screening several other contaminated surface waters were detected. ¾ Also discovered that a large share of German sewage sludges contain PFOS/PFAS (from industries, households and run off). 7 Weber R*, Bantz I**, Klumbies M**, Valentin I**, Fantke P*** *POPs Environmental Consulting, Germany **Umweltamt Landeshauptstadt Düsseldorf, Germany ***Institute of Energy Economics and the Rational Use of Energy, Stuttgart, Germany http://www.dioxin20xx.org/pdfs/2010/10-1379.pdf klu 12.08.2010 PFOS/PFAS Pollution from AFFF Use (Düsseldorf/Germany 05/2001) Germany & Federal States klu 12.08.2010 8 PFOS/PFAS Pollution from AFFF Use (Düsseldorf/Germany 05/2001) Federal State Capital Düsseldorf Area: 217 km² Population: 585 000 Inh. Population density: 2700 I/km² klu 12.08.2010 9 Ground water use in the city area of Düsseldorf/Germany Major Fire Event Extinguished by AFFF (Düsseldorf/Germany 05/2001) ¾ Düsseldorf (district Gerresheim) faced a major fire in a depot for plastic crates for beverage bottles in May 2001. ¾ The blaze was extinguished by using a 42 m3 of AFFF foam, containing perfluoroalkyl substances (PFAS) including PFOS. ¾ Assuming 1-3 % PFAS would mean a use of total 420 kg to 1260 kg PFAS in the fire event. klu 12.08.2010 10 Run-Off AFFF Contaminated Water (Düsseldorf/Germany 05/2001) Despite the ground fixation with asphalt and brick flooring at the time of the fire, PFAS in the fire water extensively infiltrated into the soil through joints and cracks, run-off from the fire place into soils boardering the area and through the partly damaged sewer system. After the fire, the depot was pulled down and the whole terrain was unsealed (2002). klu 12.08.2010 PFOS/PFAS Pollution Germany Start of National Monitoring Activities ¾For 6 years no monitoring activity at that fire place ¾2006: Discovery of drinking water contamination of rivers Möhne/Ruhr being the drinking water reservoir for 5 Million people (the main sources were PFOS/PFOA and other PFAS contaminated agricultural area) ¾Here the challenge to manage PFC contamination in drinking water works became obvious: Investment of 100 Million Euro! ¾Start of monitoring on PFAS pollution in Germany by competent authorities (2007 on) klu 12.08.2010 11 PFAS Groundwater screening in the city area of Düsseldorf (Februar 2007) PFAS Groundwater screening in the city area of Düsseldorf (End of 2007) 12 PFOS/PFAS Pollution AFFF Düsseldorf Start of Monitoring (2007/2008) Background information: Geological profile, ground water levels and surrounding of the former fire place. Former depot North Home gardens Düssel 5-6 m Backfilling GW max GW Sep. 2009 GW min Ground water flow direction klu 12.08.2010 PFOS/PFAS Pollution AFFF Düsseldorf Monitoring (2008-2010) ¾ 40 ground water samples from dedicated ground water wells and private wells from gardens were analyzed (02/2009 – 03/2010). ¾ 265 soil samples from 120 bore holes, 14 surface soil samples from vegetables gardens were taken. ¾ & Vegetable and fruit samples klu 12.08.2010 13 PFOS/PFAS Pollution AFFF Düsseldorf PFC Soil Contamination and Profile ¾ PFOS is main contaminant in the polluted soil (>90%) ¾ PFAS profile does not change significantly with depth 38 A / 1 100 390 µg/kg 38 A / 2 98 0.7 0.9 1945 µg/kg 38 A / 3 94 2.5 1.3 1.2 6412 µg/kg 38 A / 4 92 2.6 1.8 1.0 3793 µg/kg 38 A / 5 96 2.0 1.0 0.7 1765 µg/kg 38 A / 6 92 4.0 1.1 1.4 2498 µg/kg 38 A / 7 96 2.7 1.0 1350 µg/kg 38 A / 8 96 4.0 323 µg/kg Soil layer38 depth A / 9 93 3.4 1,7 0.9 1182 µg/kg PFHxA PFDA PFOS PFOA PFBS PFPA PFHpA PFBA PFHxS PFNA klu 13.01.2010 PFOS/PFAS Pollution AFFF Düsseldorf Soil and Ground Water Level (03/2010) klu 12.08.2010 14 PFOS/PFAS Pollution AFFF Düsseldorf PFC in Ground Water Vegetable Gardens ¾ PFAS profiles differ significantly from the soil samples ¾ PFOS and PFHxS are main contaminants in the polluted ground water ( together approx. >70%) 746 51300 14750 88800 14560 6100 5548 ng/l ng/l ng/l ng/l ng/l ng/l ng/l 34.85 33.14 31.19 27.03 33.65 27.87 16.58 PFNA 1.30 1.37 PFHxS 2.52 2.88 2.70 PFBA 2.25 2.30 2.14 2.30 2.03 2.93 2.73 2.10 1.99 4.75 PFHpA 3.38 1.79 6.17 3.31 4.88 2.82 4.19 5.41 4.87 4.81 PFPA 4.56 4.53 3.44 3.51 3.46 3.02 4.48 PFBS 14.75 PFOA 5.63 4.56 PFOS 41.4 51.8 42.6 42.6 66.7 37.0 PFDA 10.7 0.0 PFHxA 0.0 0.0 18.8 0.0 0.0 0.0 10.9 10.2 11.3 0.0 Distribution PFT Ground Water (%) 7.7 8.2 5.9 PZ 1 PZ 4 PZ 18 PZ 29 PZ 31 PZ 33 PZ 35 Location klu 13.01.2010 PFOS/PFAS Pollution AFFF Düsseldorf Groundwater Profile Monitoring (06/2010) ¾ For monitoring of the ground water migration from the site, 16 locations in a row distance of 7 to 8 m where measured with penetrometers (groundwater level of 3.5 m to 12 meter).
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