Document 6BzZgXbq3QQBL53gJMpdQZ98g
Environmental and Regulatory Update on Fire Fighting Foams
Tom C ortina NFPA W orld S a fe ty C onference
June 2, 2008
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O verview
* Fire Fighting Foam Coalition (FFFC) * Background * PFOS Regulations * Perfluorocarboxylic Acids (PFCAs) * EPA Global Stewardship Program * Perfluorohexanoic Acid (PFHxA) * 6:2 Fluorotelomer Sulfonate (6:2 FtS) * Aquatic Toxicity * Alternative Fuels * Wastewater Treatment * Minimizing Emissions
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Fire Fighting Foam Coalition
* FFFC is a non-profit corporation that was formed to represent the AFFF industry's interests on issues related to the environmental acceptability of fire fighting foams
* The coalition provides a focal point for industry technical reviews, development of industry positions, and interactions with the EPA and other relevant organizations
* Members are AFFF manufacturers, fluorosurfactant manufacturers, and distributors
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Fire Fighting Foam C oaiititM
Board members of FFFC: Ansul (Tyco) Chemguard DuPont Dynax Kidde (UTC)
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FFFC A ctivities
FFFC has provided EPA with information on AFFF:
> Amount of fluorosurfactant actives used in the manufacture of AFFF in the U.S.
> Chemical structure of the fluorosurfactants used in major telomer-based AFFF formulations (CBI)
> Mechanics of film formation
> Groundwater monitoring data from DoD fire training areas
> U.S. Inventory of ECF-based and telomer-based AFFF
> Overview of Foams, Market Channel, Environmental Fate
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Background
Aqueous film-forming foams (AFFF) are highly effective agents used to fight hydrocarbon fuel fires in military, industrial and municipal settings
> Aircraft Rescue Fire Fighting (ARFF) > Refinery/Petrochemical > Marine - Ships and Oil Platforms > Military - Aviation and Marine > Industrial Fixed Systems - Aircraft Hangars, Warehouse
Storage, Loading Racks, etc.
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Background
All AFFF fire fighting agents contain fluorinated surfactants (fluorosurfactants)
* Fluorinated surfactants are a key ingredient:
- no other class of surfactants can provide the required low surface tension (15 to 17 dynes/cm)
- fluorinated surfactants provide positive spreading coefficient and enable film formation on top of lighter fuels
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* Fluorinated surfactants have been produced from fluorochemicals manufactured by two methods:
- Electrochemical fluorination (ECF) - 3M
- Telomerization (telomer) - Asahi Clariant Daikin DuPont
* Only a very small percentage (3-6%) of the overall global production of these fluorochemicals has ever been used in AFFF
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* 3M only manufacturer that has stopped production of AFFF (2002)
* Fluorosurfactants in AFFF made by 3M contain and degrade into perfluorooctyl sulfonate (PFOS), which has been regulated in the US, Europe, and Canada
* Other AFFF manufacturers continue to produce AFFF for both commercial and military applications
* Fluorosurfactants in telomer-based AFFF do not contain or degrade into PFOS
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* Since 3M ended AFFF production, there has been speculation about similar environmental issues with telomer-based AFFF
* Speculation that telomer-based AFFF can break down into perfluorooctanoic acid (PFOA) or other perfluorocarboxylic acids (PFCAs) and may eventually be regulated
* Speculation that the degradation products of telomer-based AFFF may have environmental and toxic properties similar to PFOS
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PFOS Regulations
US EPA regulations do not restrict the use of existing stocks of PFOS-based (3M) AFFF
* European Union regulations require existing stocks of PFOS-based foams to be removed from service by June 27, 2011
* EU member countries must provide inventory of PFOS-based foams to EC by December 2008 - US inventory about 4.5 million pounds in 2004
Proposed regulations in Canada require existing
stocks of PFOS-based AFFF to be removed from
service 5 years after regulation is final (2013)
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PFCAs
Telomer-based AFFF is not made with PFCAs
* In October 2003 an EPA workgroup determined that telomer-based foams are not likely to be a significant source of PFCAs in the environment
* EPA workgroup concluded that existing data "provided no evidence that these fluorosurfactants biodegrade into PFOA or its homologs..."
* Telomer-based AFFF may contain trace levels of
PFCAs such as PFOA and perfluorohexanoic acid
(PFHxA)
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Global Stewardship Program
* EPA is addressing emissions of PFCAs through a global stewardship program
* Under the EPA program, telomer manufacturers are working towards elimination of trace levels of PFOA, PFOA precursors, and related higher homologue chemicals from finished products by 2015
* Confirms FFFC's message of last 7 years that EPA is unlikely to ban or severely restrict the use of telomer-based products such as AFFF
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Im pact o f EPA Program
EPA stewardship program is focused on eliminating telomers with eight or more carbons (C8 or above)
The majority (over 75%) of the fluorosurfactants used in telomer-based AFFF are derived from six-carbon molecules (C6)
Some current AFFF formulations contain over 95% C6-based fluorosurfactants, but others contain a higher percentage of C8and above
Higher homologue chemicals can provide some positive characteristics related to foam effectiveness
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Im pact o f EPA Program
In order to comply with the EPA stewardship program, manufacturers will be introducing new or reformulated products over the next few years that contain only C6-based fluorosurfactants
New products are expected to retain all of the same fire suppression capabilities as existing AFFF agents
New products would be expected to contain less fluorine and have a smaller environmental impact
Changes to formulations may require products to be re-qualified under the milspec or other specifications
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PFHxA
* Telomer-based AFFF may contain trace levels of perfluorohexanoic acid (PFHxA), which are not being addressed by the EPA stewardship program
* Although we know of no direct evidence, it is speculated that telomer-based AFFF may break down in the environment to PFHxA*
* Extensive data presented at an EPA information forum in June 2006 and at the Reebok conference in September 2007 provides a very favorable initial toxicology profile for PFHxA
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6:2 FtS
It has been determined based on groundwater
monitoring studies that the 6:2 fluorotelomer
sulfonate (6:2 FtS) is likely the primary breakdown
product of the C6fluorosurfactants contained in
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Recent studies on AFFF-type surfactants likely to break down to the 6:2 FtS show the following:
- Low in acute and sub-chronic toxicity
- Low in aquatic toxicity
- Negative for genetic and developmental toxicity
- Not bioaccumulative according to regulatory criteria
- Significantly lower than PFOS in biopersistence
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Aquatic Toxicity
* Toxicity assessment for fire fighting foams focuses on aquatic species
* Less effective fire fighting foams that do not contain fluorosurfactants (fluorine-free) are often marketed as being environmentally friendly
* To directly compare different agents, FFFC sponsored aquatic toxicity testing of six different commercially available fire fighting foams
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Aquatic Toxicity
Agents tested:
> Wetting Agent > Fluorine-free Foam A - 3% concentrate > Fluorine-free Foam B - 3% concentrate > Milspec AFFF - 3% concentrate > AR-AFFF - 3% concentrate > UL AFFF - 3% concentrate
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Aquatic Toxicity
96-Hour LC50 Test in Fingerling Rainbow Trout
Agent
Wetting Agent Fluorine-free Foam A Fluorine-free Foam B Milspec AFFF AR-AFF UL AFFF
LC50 (mg/L) 1.06 65 71 2176 3536 5657
Lower number = higher toxicity
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Aquatic Toxicity
96-Hour LC50 Test in Fathead Minnows
Agent
LC50 (mg/L)
Wetting Agent Fluorine-free Foam A Fluorine-free Foam B Milspec AFFF
0.887 171 171 884
AR-AFF
1487
UL AFFF
1726
Lower number = higher toxicity
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Aquatic Toxicity
* Not surprising that fluorine-free foams would have higher aquatic toxicity than AFFF
* Contain higher concentrations of hydrocarbon surfactants and solvents, which are more toxic than fluorosurfactants
* Milspec AFFF has more hydrocarbon surfactants and solvents than AR-AFFF, AR-AFFF has more than UL AFFF
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Aquatic Toxicity
Just because a fire fighting foam does not contain fluorosurfactants does not mean that it is less toxic or more "environmentally friendly"
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A ltsm ativB FubIs
Increased use of alternative fuels, especially ethanol, raises concerns related to the use of different types of fire fighting foams
In response to these concerns the industry organized the Ethanol Emergency Response Coalition (EERC)
EERC sponsored testing of six different types of fire fighting foams against two different ethanol fuels
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A lternative Fuels
Ethanol Emergency Response Coalition (EERC) - Alternative Fuels Testing Program
> Foam Agents >AR-AFFF, AFFF, AR-FFFP, FP, class A foam, emulsifier
>Test Protocol >UL 162 - topside and sprinkler testing
> Fuels Tested >Denatured ethanol (E95) and gasohol (E10)
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A lternative Fuels
EERC Testing Results
> Denatured ethanol (E95) fires are most effectively extinguished with AR type foams (AR-AFFF & AR-FFFP)
>Gasohol (E10) fires may be extinguished using AFFF or AR-AFFF, but increased application rates may be necessary for burn back resistance
> AR-AFFF was the only agent that was successful in all fire test scenarios
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Wastewater Treatment
Oil refinery in Missouri had fire in bulk plant resulting in 1.1 million gallons of wastewater containing gasoline, diesel fuel, combustion byproducts, fire fighting foam agents
State DNR issued a Hazardous Substance Emergency Declaration requiring characterization and removal/disposal
Company contacted FFFC for help in dealing with the fluorosurfactants in the wastewater
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Wastewater Treatment
* Dr. Martial Pabon of DuPont has done research on treating water contaminated with fluorosurfactants using activated carbon
* Company successfully treated 1.1 million gallons of wastewater in 15 days using granular activated carbon (GAC) in a trailer-mounted system
* Dr. Pabon believes that similar operation could be performed without having to pump the foam by using a different type of activated carbon
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Wastewater Treatment
Dr. Pabon has done additional research on other methods to treat wastewater, including nanofiltration, ultrafilitration, and reverse osmosis
* 30 million liters of wastewater from Buncefield fire contaminated with PFOS-based and telomer-based foams has been treated using GAC, reverse osmosis, and other methods
* Always major clean-up issues after a large oil fire
* Fluorosurfactants do not present a unique problem
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M inim ize Emissions
Follow applicable industry standards on the design, installation, and maintenance of foam systems and extinguishers
* Minimize false discharges from fixed foam systems by using approved detection, actuation, and control systems as required by industry standards
* Use non-fluorosurfactant training foams
* Provide for containment, treatment, and proper disposal of foam discharges
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Sum m ary
* Telomer-based AFFF agents are persistent, but are not generally considered to be significant environmental toxins
* Major perceived threat to the future of telomerbased AFFF was that it could break down in the environment to PFCAs and would eventually be regulated by EPA
* EPA is addressing emissions of PFCAs through a voluntary global stewardship program
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Sum m ary
* Some reformulation of AFFF fluorosurfactants in the next few years to comply with EPA program
* Expect new agents to have same or increased effectiveness with reduced environmental impact
* Recent testing shows that alcohol resistant foams (AR-AFFF) provide the best extinguishment of ethanol-based fuel fires
* Wastewater containing fluorosurfactant foams has been effectively treated using GAC, reverse osmosis, and other membrane processes
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* FFFC is pleased to provide information on AFFF:
Fire Fighting Foam Coalition (FFFC) 2111 Wilson Boulevard, 8th Floor Arlington, VA 22201 703-524-6636 cortina@alcalde-fav.com www.fffc.org
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