Environmental occurrence and risks of …

1 Environmental occurrence and risks of perfluoroalkyl substances ( pfas ) Timo Sepp l Senior adviser Finnish Environment Institute European Conference of Defence and the Environment Helsinki, June 10, 2015 Introduction to perfluorinated compounds Main emissive uses Fire-fighting foams Water and stain repellents Metal plating Hydraulic fluids in aviation Regulation Findings in different countries Conclusions Contents What are they? Polyfluorinated chemicals Polyfluoroalkylated substances (PFCs) belong to a large and complex group of organic substances that are extremely versatile and used in a variety of industrial and household applications. The main characteristics of the polyfluorinated compounds are the replacement of most hydrogen by fluorine in the aliphatic chain structure.

2 Some of the organic fluorine compounds are known as perfluorinated, which means that all hydrogens have been replaced with fluorine. PFCs are synthetically produced compounds which do not occur naturally, and have been manufactured for over 50 years. Mostly used as a surface-active agent and in a variety of products, such as fire fighting foams, carpets, leather/apparel, textiles/upholstery, paper and packaging, coatings and coating additives, industrial and household cleaning products, paints, pesticides and insecticides. Dozens of different chemicals with different properties for different uses pfas are exceptionally stable chemicals in the environment PFOS not known to degrade in any natural conditions Can be toxic (especially reproduction and development) The scientific and regulatory communities are beginning to investigate, understand, and effectively manage polyfluorinated compounds and their impacts.

3 pfas introduction continues Examples Fire-fighting foams Water and stain repellent treatment Metal plating Aviation hydraulic fluids Main uses of pfas thought relevant for the military Aqueous film forming foam (AFFF) are unique amongst other fire-fighting foams in that they contain a small percentage of fluorinated surfactant (fluorosurfactant) US military: 11 million liters stockpile in 2004 (29%) Military specifications may differ from other civil uses Used by fire-brigades as well as in fixed installations, such as airplane hangars Specific contents poorly known Not all fire-fighting foams are pfas -based Fire-fighting foams Fluorinated finishes are a technology known to deliver durable and effective oil and water repellence and stain and oil release properties.

4 Outdoor clothing, tents and other performance textiles Historically, fluorinated polymers based on perfluorooctane sulfonyl (PFOS) PFOS was not directly used to treat textiles but used to be present at up to 2 wt % in products. Now the industry is moving from C8 to shorter chain-length chemicals (C6, C4) Non-fluorinated alternative technologies such as hydrocarbon waxes and silicones can provide durable water repellence but not oil repellence or soil and stain release The impregnation facilities may be a significant source Water and stain repellent treatment PFOS is a surfactant, wetting agent and mist suppressing agent for hard chrome plating (Cr-6) Alternatives to PFOS being phased in: In Europe common alternative is 6:2-Fluorotelomer sulfonate (6:2 FTS).

5 It can slowly degrade to perfluorocarboxylic acids such as perfluorohexanoic acid (PFHxA). May be a significant point source Metal plating PFOS-related substances or precursors have been used as an additive to the aviation hydraulic fluids with a content of about or less than Other fluorinated chemicals may be used as well According to the manufacturers, this formulation helps prevent evaporation, fires, and corrosion Aviation hydraulic fluids without fluorinated chemicals are used, but based on , , phosphate esters. These substances can absorb water and the subsequent formation of phosphoric acid can damage metallic parts of the hydraulic system. Aviation hydraulic fluids PFOS is globally highly restricted, PFOA in the pipeline Studies have found PFOS and PFOA in the blood samples of the general human population and wildlife worldwide, indicating that exposure to the chemicals is widespread Because of their persistence and long-term accumulation, higher trophic level wildlife such as fish, piscivorous birds and other biota can continue to be exposed to PFOS and PFOA pfas regulation 1/2 Studies also indicate that continued exposure to low levels of PFOA in drinking water may result in adverse health effects readily absorbed after oral exposure and accumulate primarily in the serum, kidney and liver.

6 No further metabolism is expected Acute- and intermediate-duration oral studies on rodents have raised concerns about potential developmental, reproductive and other systemic effects of PFOS and PFOA Other pfas widely found in the environment as well pfas regulation 2/2 PFOS being replaced after 50 years of use Many pfas are highly persistent in the environment, some undergo transformation Mostly not volatile, some (such as FTOH) semi-volatile Short-chain pfas are generally more mobile than their long-chain homologues they are not retarded in soil and have already been detected in groundwater Long-chain pfas more bioaccumulative Among all Environmental media, open ocean water is likely the largest global reservoir of pfas Many countries have screened pfas in the environment close to potential sources Environmental Quality Standards are easily exceeded When released into the environment Prior to 2000, the majority of the fluorosurfactants used in the AFFF were PFOS-based which resulted in AFFF that contained PFOS and PFOS precursors.

7 The primary supply of AFFF then became fluorotelomer-based, that will during use or presence in the environment degrade to the basic pfas such as PFOA and its homologues. The current effort is to replace these PFOA based long-chain fluorosurfactants with shorter-chain fluorosurfactants such as perfluorohexylethanol [6-2 FTOH] derivatives C8-based PFCs phased out by many manufacturers before 2015 The specific identities of replacements or substitutes for PFOS,PFOS-related chemicals and mixtures have been claimed as confidential business information. Very difficult to find out what is used Big question: what is in the AFFF? From: Stockholm Convention POPRC (UNEP/ ) PFOS and PFOA and a number of other pfas have been detected in North America and Europe in surface water and sediments downstream of former fluorochemical production facilities in wastewater treatment plant effluent sewage sludge and landfill leachate airports and fire fighting drill areas Reverse Fire fighting drill area pfas in soil and GW Stockholm Convention POPRC review on alternatives to PFOS 2012.

8 There is little or no independent and reliable information publicly available on the toxicological and ecotoxicological characteristics of alternatives to PFOS and its related compounds, with the exception of perfluorohexanoic acid (PFHxA) and perfluorobutanesulfonic acid (PFBS) and their related compounds Consequently, for several reasons, it is currently not possible to perform comprehensive risk assessment on most of the alternative applied chemicals to PFOS and related compounds. Perfluorohexane sulfonyl fluoride (PFHxSF) and its derivatives are not feasible alternatives due to similar characteristics as PFOS and related compounds. What about the risks ? Long-term source of pollution PFOS and PFOA found worldwide in human blood and biota pfas have many uses Exact composition often proprietary information Difficult to know exactly what is being used MSDS: fluorochemical 0,5-25% The most harmful known (C8 based) perfluoralkylic acids being phased out AFFF-use has contaminated groundwaters and soils above Environmental quality standards Textile, paper and leather impregnation and metal plating facilities may be a significant point source Conclusions