Aqueous FilmForming Foam AFFF Learning Objectives Describe foam

Aqueous Film-Forming Foam (AFFF)

Learning Objectives Describe foam classes, fluorinated and fluorinefree, and foam composition Understand Learn the AFFF release mechanisms AFFF regulations and ongoing research Become familiar with best management practices (BMPs) for: ü Procurement and Storage ü Use and Replacement ü Treatment and Disposal

Classes of Firefighting Foams CLASS A Foams- Developed in the 1980 s for fighting wildfires and used structure fires. Do not contain PFAS CLASS B Foams- Used fight fires involving flammable and combustible liquids and gases; petroleum greases, tars, oils and gasoline; and solvents and alcohols Several Class B foams contain PFAS AFFF are the primary Class B foam that contain fluorosurfactants Source: S. Thomas, Wood plc, used with permission from Aqueous Film-forming Foam Fact sheet (ITRC, 2018)

Types: Legacy PFOS AFFF ECF chemistry Homologous series (C 2 -C 13)1 Branched & linear isomers (30: 70)2 If exclude branched isomers, concentrations underestimated (biased low) Crude synthesis, many side products PFAS composition 89% PFSAs (e. g. , PFOS) in 3 M AFFF 1. 6% PFCAs (e. g. , PFOA) 9. 4% other forms with multiple charged groups branched isomers Photo courtesy of J. Field linear isomer zwitterionic (+/-) Figure courtesy C. Higgins, Colorado School of Mines 1 Barzen-Hansen et al. , 2015. ES&T Letters 2: 95 -99; 2 Benskin, 2010. Rev Environ Contam Toxicol

Types: Legacy Fluorotelomer AFFFs 1 Polyfluorinated forms Do not contain PFOS or degrade to PFOS n = 6, 8 Angus (1994) None listed on UMCR 3 or Method 537 lists Precursors with -Sdegrade to fluorotelomer sulfonates and PFCAs 1, 2 n = 6, 8 Ansul (1970), Angus (1994), Chemguard (2002) n = 4, 6, 8, 10, 12 National Foam (1976), Fire Service Plus (2002) n = 6, 8 National Foam (1976), Fire Service Plus (2002) n = 5, 7, 9 Buckeye (2002) 1 Place n = 5, 7, 9 Buckeye (2002) and Field, 2012. ES&T 46: 7120 -7127; 2 Weiner et al. , 2013. Environ Chem 10: 486 -493; 3 Harding-Marjanovic et al. , 2015. ES&T 49: 7666 -7674 Photo and diagrams used with permission from J. Field, Oregon State

Types: Modern Fluorotelomer AFFFs In response to EPA 2010/2015 Voluntary PFOA Stewardship Program Should contain almost exclusively short-chain PFAS (C 6) Little or no data on toxicity and bioaccumulation of polyfluorinated substances, assumed to be less toxic and bioaccumulative due to shorter chains 1 May still contain trace quantities (ppb levels) of PFOA (or precursors) as byproducts of the manufacturing process Polyfluorinated substances biodegrade to persistent transformation products (e. g. , perfluoroalkyl carboxylates) 2 USEPA 2018. “Risk Management for Per- and Polyfluoroalkyl Substances (PFASs) under TSCA. ” https: //www. epa. gov/assessingand-managing-chemicals-under-tsca/risk-management-and-polyfluoroalkyl-substances-pfass. (Accessed August 2018). 2 Scheringer et al. . 2014. “Helsingør Statement on poly- and perfluorinated alkyl substances (PFASs). ” Chemosphere. 114: 337 -339. 1

AFFF Contains Highly Diverse Mixtures AFFF product chemistry has changed over time 1989 3 M AFFF PFS Ansul AFFF 4: 2 Ft. TAo. S PFS 6: 2 Ft. TAo. S PFCA 8: 2 Ft. TAo. S PFSa. Am 1993 -2001 3 M AFFF PFSa. Am. A Ft. S Barzen-Hanson et al. 2017. Environ Sci Technol 51: 2047 -2057 Figures used with permission from J. Field, Oregon State

Typical Composition of AFFF products also contain other surfactants, solvents, additives 3% AFFF concentrate contains: More than 60% water/diluent Up to 20% is solvents As much as 18% is surfactants of which less than 2% is fluorosurfactants. >60% Water/Diluent <20% Solvents 15 -18% Surfactants with <2% Fluorosurfactants Source: S. Thomas, Wood plc, adapted from Kempisty, Xing and Racz 2018 Additives & Modifiers 8

Mechanisms for Release to Environment Foam is released via various practices and mechanisms: low volume releases of foam concentrate during storage, transfer or operational processes accidental leaks from foam distribution piping between storage and pumping locations and from storage tanks and railcars moderate volume discharge of foam solution for apparatus testing and episodic discharge of AFFF-containing fire suppression systems occasional, high-volume, broadcast discharge of foam solution for firefighting and fire suppression/prevention for emergency response periodic, high volume, broadcast discharge for fire training 9

Mechanisms for Release to Environment AFFF is applied by mixing concentrate with water The foam solution is aerated at the nozzle Once released, it can contaminate soil, surface water and groundwater Co-contaminants often present Source: Adapted from figure by J. Hale, Kleinfelder, used with permission 10

Mechanisms for Release to Environment Source: Adapted from figure by L. Trozzolo, TRC, used with permission 11

AFFF Procurement and inventory Foam Selection and Requirements Document HAZARD Anything that has the potential to cause harm all procurement and inventory RISK How great are the chances someone or something will be harmed by the hazard Understand performance specification requirements (e. g, Mil-Spec MIL-PRF-24385, UL Standard 162, etc) Concentrate mixtures of 1, 3, or 6 percent solution with water Foam Storage and Handling Stored in 5 - gallon bucket, 55 -gallon drum to 256 -gallon container, 5000 -gallon tanker truck, or suppression system Ensure proper secondary containment to avoid spills/mishaps Adapted from https: //worksmart. org. uk/health-advice/health-andsafety/hazards-and-risks/what-difference-between-hazard-and-risk 12

Foam Systems and Operation Fixed System Testing Design should incorporate containment, collection, and run-off components Systems connected to city water should be fitted with back-flow prevention Some codes (e. g. NFPA Standards 16 and 25) require testing Consider alternatives for testing (e. g. testing with water, etc. ) to minimize or eliminate environmental release Check applicable regulatory requirements 13

Foam Systems and Operation Mobile Fire Equipment Testing Includes Some extinguishers, vehicles, marine craft, etc. codes (e. g. NFPA Standards 412 and 2020) require testing Consider Using alternatives for standard outdoor testing methods water for testing Testing equipment indoors Spraying into drums or other containers Testing in lined pits/spill containment Testing with Closed-Loop systems (per FAA Cert Alert 19 -01, FAA 2019) 14

Foam Systems and Operation Training Exercises at Fire Training Areas Design should incorporate containment, collection, and controlling run-off of foam and unburned fuels Consider alternatives for testing Using water or fluorine-free foams for testing Avoid testing in adverse weather (high winds) Keep spraying to restricted targeted areas 15

Emergency Firefighting Operations Pre-planning essential to minimize release of spent fire water containing AFFF and other contaminants Any discharge to public waters may be subject to remediation requirements under CERCLA 42 U. S. Code § 9601 Emergency scenarios vary and need careful consideration Industrial Oil processes with fixed systems refineries with large aboveground storage tanks Remote sites with no immediate threat to life or property 16

Emergency Firefighting Operations Personal Protective Equipment Self-Contained Breathing Apparatus (SCBA) or positive pressure supplied air respirator (SAR) is recommended Wear appropriate turnout gear Place in bag and containerize when removed Wash with warm water and avoid use of fabric softeners or bleach Never wash in home washing machines Avoid hand to mouth contact and wear gloves when handling Potential Consult environmental impacts with laundering regulatory agencies to determine BMPs 17

Emergency Firefighting Operations Initial mitigation efforts for firefighting foam Consider developing a fire response plan in advance Source control limit the spread of foam and fire water by eliminating source Identify sensitive areas (water systems, storm drains, surface water, critical habitat) Containment Identify potential source areas, pathways, receptors for spill kit placement Minimize Initial tactics footprint with berms, dikes, blocking drains or outlets etc. recovery tactics Utilize pumps or vacuum trucks to remove concentrate, excavate saturated soil 18

Immediate Investigative and Clean-Up Actions Visual site delineation- take photos and use pin flags to outline affected area Shake test- use test to qualitatively identify media (soil or water) containing high concentrations of AFFF product Initial investigative sampling - use to determine nature and extent and need for additional characterization Interim media removal - use for hot spot soils removal to reduce migration to other Confirmation samples- use to confirm interim removal successful or need for additional remedial actions 19

Treatment and disposal Best management practices include accounting for all volumes of AFFF and weights of system components for disposal certificates. AFFF concentrate should be incinerated at 1, 000 degrees C Fire and Flush Water Containing AFFF should be disposed of as a generated waste Water can be reduced and concentrated prior to disposal to reduce treatment costs Concentrated stabilized waste can be incinerated, landfilled, or 20

Firefighting Foam and Foam System Replacement Consider performance specifications, system requirements and modifications, decontamination and disposal Replacement Products Fluorine-free foams (F 3) - not all created equally, evaluate carefully Modern fluorotelomer foams - still contain ppb level concentrations of PFOA and precursors System decontamination and sampling during foam replacement Currently no regulatory guidelines for clean-out Do. D requires triple-rinse after AFFF foam product has been removed Some system components may need to be disposed of, replaced, and managed as waste material Confirmation sampling required to ensure residual concentrations are below regulatory criteria 21

Federal, State Regulations and Guidance FAA Reauthorization Act of 2018 (HR 302)- signed Oct. 5, 2018 -allow use of F 3 within 3 years New York 6 NYCRR Part 597 identifies PFOS/PFOA as hazardous substances Includes storage and registration for class B foams and reporting for spills (NYDEC 2017) Prohibition of PFAS in firefighting foams MI, KY, VA- prohibition for training only WA (with exceptions), MN, NY, CT -policies on AFFF Take-Back Programs Open source image from Royalty Free Stock Photos Several states (MA, NY, VT, MI) have programs to assist fire departments in the proper disposal of legacy firefighting foams It includes the identification and disposal of legacy foams Massachusetts Department of Environmental Protection (May 2018). https: //www. mass. gov/news/commonwealth-begins-program-toremove-legacy-firefighting-foams-from-fire-department New York Department of Environmental Conservation (NYDEC). 2017. Hazardous Substances Identification, Release Prohibition, and Release Reporting. Effective March 3, 2017. http: //www. dec. ny. gov/regulations/104968. html Washington Senate Bill 6413 (2018). Engrossed Substitute Senate Bill 6413. 65 th Legislature 2018 Regular Session. March 5 2018

International Regulations and Guidance Canada January 2018 - Prohibition of manufacture, use, sale, or import of several PFAS products such as AFFF. Exemption for military and airport use June 2019 - Transport Canada Exemption for Airports - allowed to use F 3 in lieu of AFFF Germany 2013 - Release of Guidance on environmentally responsible use of AFFF Australia July 2016 - Queensland Govt issued operational policy on environmental management of fire fighting foam Massachusetts Department of Environmental Protection (May 2018). https: //www. mass. gov/news/commonwealth-begins-program-toremove-legacy-firefighting-foams-from-fire-department New York Department of Environmental Conservation (NYDEC). 2017. Hazardous Substances Identification, Release Prohibition, and Release Reporting. Effective March 3, 2017. http: //www. dec. ny. gov/regulations/104968. html Washington Senate Bill 6413 (2018). Engrossed Substitute Senate Bill 6413. 65 th Legislature 2018 Regular Session. March 5 2018

Foam Research and Development SERDP-ESTCP Research (https: //serdp-estcp. org/) Novel Fluorine-free Replacement for AFFF – NRL- (completion August 2018) Fluorine-free 2019) Foam- National Foam- (completion September Fluorine-free Foams with Oleophobic Surfactants and Additives for Effective Pool Fire Suppression- NRL- (completion December 2020) 24

Foam Research and Development Other On-going Efforts Petroleum Environmental Research Forum (PERF), 2016 Firefighting Foam Human Health and Environmental Risks at O&G Operations (Integral Consulting and Wood). European Chemicals Agency, 2019. Assessment of Alternatives to PFAS-containing Fire-fighting Foams and the Socio-economic Impacts of Substitution (Wood and COWI). European Commission, 2019. The Use of PFAS and Fluorinefree Alternatives in Fire-fighting Foams (Wood and Ramboll). 25

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