Document mkQyn05rY4Z6GwjMQrmLQ2kQ
DoD MERIT Crystal City, VA 19 July 2016
Stephen Korzeniowski
Introduction Emerging Issues Historical Perspective Transition to Short-chains Regulatory Update
- United States - Australia
Fluorine-free Foams Foam Legacy Consequences Best Practice Guidance - FFFC Current Events & Summary
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37+ Years at DuPont/Chemours Organic Chemist by Training - PhD; M BA-Finance 26 Years in Fluorochemical Technology & Business Roles 15 Years in AFFF Fluorochemcials (2001 - Present) Led DuPont Fluorotelomer technology & plant transition from long to
short chains and in US EPA Stewardship Program Founding Member and Past Chairman and Board Member of FFFC Founding Member and Previous Chair of Telomer Research Program
(TRP: 2000-2011) and FluoroCouncil Member (2011 - Present) Co-author of 45+ Papers & Articles in Organic Synthesis, Analytical,
Toxicology and Fluorotechnology Started BeachEdge Consulting one year ago following Chemours exit
- Consult for various companies and teach at local university
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US Department of Defense Federal Aviation Administration European Commission Environment Canada Canadian Department of National Defence Belgian Environment Agency Queensland Department of Environment Western Australia Department of Environment China Ministry of Environmental Protection Stockholm Convention on POPs UK Civil Aviation Authority Global approval bodies: US EPA, METI, UBA
KEM
SiMidllli Owisil'i Afeeef
Environment
Canada
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In Business it is the 4 P's of Marketing: - Product, Place, Price, Promotion - Other P's are Positioning, People, Profit
In Fluorochemistry (P FA S 's) the P's have evolved as the chemistry has changed from long-chains to short chains - The discussion/debate has shifted away from PBT as the chemistry has changed
The 4 P 's of Fluorochemistry: - Potential, Precaution, Presence, Persistence (or vP)
A critical P that must always be added to this equation is: Performance
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Need to better understand the degradants or metabolites from the short chain C6 chemistry: PFHxA plus......
Misconception that all PFASs are the Same - long chain, short chain - all have CF Bond
- Simplistic view by some Parties is they are all the same (which they are clearly not) and should be treated as such
Drinking Water
- Evolving situation primarily as a result of the US EPA Health Advisory on PFOS and PFOA
- Military bases - "Flint, Michigan" effect
Criteria Changing
- Heightened focus on Precautionary Principle - Set aside "risk based" approach and assessments - Development of new criteria of concern: PMT and vP vs PBT - Overt focus on Mobility and Persistence as critical criteria
Not T & B as in PBT
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Ta iraa ini 'Ss ui tmi orani t wo %S*aha%o*ar at,- c%*haaaaianaa&sm: aEmmaaaae^ar aogianaaaj ai sf-ssauaaea^ss
Headlines: Precautionary Principle and "Reversibility of Exposure"
Both Australia QLD DEHP and Cousins et al have invoked the precautionary principle as the basis for their published positions
Germany and Cousins et al are also focusing on PMT vs PBT with P being given significant weight and Mobility (M) replacing B in the evaluation process
Reversibility of Exposure: Environment & Human Body Precautionary Principle vs Risk-based Approach
Madrid & Helsingor Statements: Blum & Cousins Green Science Policy Institute: Blum
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Industry phase-outs and replacements
Products (low molecular weight and polymers) containing long-chain perfluoroalkyl moieties
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University
FF, FF. FF,
F, F r F F, F Scan F.
F F F F F' F
fp iy r F' F F F F
PFSAs (> 6 perfluorinated carbons)
PFCAs (> 7 perfluorinated carbons)
F FF FF FF
FF FF F
8:2 FTOH
V
Mainly replaced with alternative products containing or
degrading to form
Short-chain PFAS moieties
PFGA < 7 p e r f lu o r in M r r f | : | J PF3A < 6 peril uorinaiea carBons* '
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IS
- From presentation by Ian Cousins at May 2016 Helsinki Chemicals Forum and June 2016 Workshop "Strategy for a Non-toxic Environment of the 7th Environmental Action Programme (EAP)"
........ .
"To protect groundwater resources for future generations, society shouid consider a precautionary approach to chemicais management and prevent the use and reiease of highiy persistent and mobile chemicals such as PFASs."
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Green Science Policy Institute (author of Madrid Statement)
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QPL Products and Suppliers
1985
1990
1995
\
Initial in 1969
3VI
Initial in 1974 (Ciba-Geigy)
Ansul
Initial in 1973, then 1981
National foam
Modified from Field & Place, Environ. Sci. Technol. 2012, 46, 7120-7127
2005
2010 Ciment
A u lii'
Buckcvc KSP
QPL History. Nov 1969 Spec MIL-F-24385 Issued. First QPL Approval to 3M's FC-196. The first AFFF for Naval Fire Service was 3M's FC-183, Introduced in 1964. FC-183 was Later Replaced with FC-194 and then FC-195
From NRL Report 7437
Fire Fighting Foam Coalition Members:
The Industry Has Changed
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Fluorotelomers (Telomerization)
CF2=CF2
I
(TFE)
Perfluoroalkyl Iodide
n = 4,6,8,10,12, even
F(CF2)nC H X hM Fluorotelomer Iodide
-- 1 F(CF2)nCH2CH!S 03X: FT Sulfonate -- AFFF Surfactants 'r
F(CF2)nCH2CH2OH
I Fluorotelomer Alcohol
Sales Products
Even number, straight chains, No Branching Polymers n> 8 ; Surfactants n=6 primarily By YE 2015 n <6
ECF (Electrochemical Fluorination)
H(CH2)nSH
PASF = Perfluoroalkylsulfonates
F(CF2)nS 0 2F
F(CF2)nS 0 3X
PFOS n = 8; ... PFHXS.n.=.6...
PFBS n = 4
F(CF2)nS 0 2N(R)CH2CH2OH
Perfluoroalkyl sulfonamido ethanol
Sales Products
ECF produced materials have up to 30% branched isomers at the fluorinated chain end and contain odd and even carbon chain lengths
'lilt
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CF2=CF2
i
F(CF2)6I
I
(TFE)
F(CF2)6CH2CH2I
Fluorotelomer Raw Materials
Perfluorohexyl Iodide
6:2 Fluorotelomer Iodide
F(CFo)cCHoCHoSOoCI 6:2 Fluorotelomer Sulfonyl Chloride
' 2 ,6 2 2 2
(6:2 FTSC1)
F(CF2)6CH2CH2OH 6:2 Fluorotelomer Alcohol
Polymeric and
Surfactant Commercial
Products
F(CF2)6CH2CH20 C (0)C (C H 3)=CH2 6:2 Methacrylate
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B
Fluorotelomer -Based:
A-G
6:2 FtSaB 8:2 FtSaB 1Q:2 FtSaB 12:2 FtSaB
Ftuorote'lomerS.ulfanarriidd Ani:inesN o- .
HH*'" 63 FtSaAnt
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Fluorotelomer Betaines1'
5:1:2 FIB 7:1:2 F tft 9:1:2 FtB
5:3 FtB
7:3 9:3
FIB FtB
Fluorotelomer Sulfonates1
4:2'FtS
6:2 8:2
FtS FtS
The Chemistry: 1960's - Present
ti= 4
wn==68'
at St} at
Perfluoroalkyt SuIfonamtdo AminesN r- PFBSaAm n = 4 Ql
Ql-Q . PFPeSaAtn n = 5
jy II Q"
PFHxSaAm n-= fi Ql
PFHpSaAm! n =-7 Ql
n=6 Sq
PFOSaAm n-~ i ; Qi
g q Perftuoroajky! Sulfonamide Amino Carboxylates^
n=fi St| n= 8 Ql n M Ql n 12 Ql
:IGI fi1Q
O \-H N -
PFBSaAmA PFPeSaAmA PFHxSaAmA PFHpSaAmA * PFOSaAmA
n :=4-
nr:a=5$-
Ql Ql Ql Ql Ql
Peril uoroalkyl Sulfonates1
PFBS .it= 4 cm-
n=6 n=M
aStt}
0
{]
S-- O
5
'
PFPeS*
PFHxS
PFHpS
PFOS
PFN5 +
PFBS-
n -=-S Ql
rv= 6 Qn
nn~= 78
cm
Q;n
n-= Ql
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n = 5 St,
n = 7 Sq
n = 3 Sq
fi ;n
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S:q
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r--4 Qrr
n:= 6. On
h:= S- Qn
PerflufiroalkylCarhoxylates1
:PF!A n= 4 Qn
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F --C ---C1--O
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n
'.PPFFHPexAA PFHpA
-PFQA
;PFNA
pfda
PFU.dA.
PFDdA
n= 5 Qn
n=6 Qn
n=7 Qn
n= S Q n
n=i "Qn:
n = 10 Qn
n==1121 QQnn
P F trA
b = i t Q;n
'PFteA
i=J4 On
Backe, Day & Field: ID Letters from: B.J. Place and J. A. Field, Environ. Sci. Technol. 2012, 46, 7123
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F ro m 2S1a A C S N a tio n a l Cfoatm gi OAa C h a im A E n v M H a r d i 1 3 d ? t 2318
Dynax Fluorotelomer Betaine
L Jn '
n=5,7,9
DX3001*:
RfCHFC2H4N+(CH3)2CH2COO- -80% RfCH2C2H4N+(CH3)2CH2COO- - 20%
Rf Distribution (average): C5 C7 >C9 45.4% 40.8% -13.8%
^Production phased out in 2014
Ref: Fig. F&G: B.J. Place and J. A. Field, Environ. Sci. Technol. 2012, 46, 7123
Is ,, iio r t- c h iJ n c h e m is try n e w ?
No. key component of some foams since the 1970s
AFFFs with >95% short-chain fluorotelomer-based fluorosurfactants have been on market for >30 years and exceed the most challenging industry standards
AFFFs with >95% short-chain fluorotelomer-based fluorosurfactants have been primary foams used for last decade by US, Australian, and European armed services
New mil-spec AFFF agents from ICL, National Foam, Solberg, and Tyco containing only short-chain fluorotelomer-based fluorosurfactants
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1963 1964
Tuve + Jablonsky, US NRL, 3M/NRL Collaboration
PFOS + PFOAtype fluorosurfactants Light Water + Purple K (Twin Agents) (no hydrocarbon surfactants) MIL-F-23905 (11/1/63) (Fresh water only)
Ratzer, Chemical Concentrates: Use of Hydrocarbon Surfactants with fluorosurfactants in AFFF
1967 USS Forrestal Fire
1969
3M Francen Patents: Use of Hydrocarbon Surfactants with Fluorosurfactants in AFFF
1969 1972-75 1973
MIL-F-24385 (6% AFFF) (Fresh & Seawater)
Atochem, France & Ciba-Geigy, USA: 6:2/8:2 and 6:2 FT-Surfactants for AFFF Aaents Pilot plant production for AFFF agent tests at Eau et Feu (Atochem) and Ansul (Ciba-Geigy)
First AR-AFFF launched by National Foam
1978 DC-10 Aircraft Fire at LAX
1982-
Large selections of 6:2 FT-Surfactants available to AFFF agent producers for US Mil-spec applications
US 3,258,423 (filed 9/4/63) GB 1,070,289 (filed 9/3/64)
Campobello Foam Meeting (10/11-13/64). Published in "FoanT Oct. 1964. Nr. 24 Protein Foam used; 134 dead/62 injured/21 aircrafts destroyed US 3,562.156 (filed 6/12/69) US 3,772.195 (filed 2/5/71): Invalidated 1980 Seawater tests introduced
' Forafac' (Atochem) and "Lodyne" (Ciba-Geigy) (C6 purity > 95-97%)
3M's Light Water used 196 lives saved out of 200
6:2 FT-surfactants: C6 ( > 95-97%) + C4 & C8
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Fluorosurfactants for Firefighting Foams
Key Events 1990 - 2015
1991
Dynax is founded and starts fluorotelomer surfactant R&D.
1993-1995
2000-2002
Dynax introduces C5/C7/C9-based fluorotelomer surfactant (DX3001), and 1st and 2nd generation all C6 (>99%) foam stabilizers: DX4302 & DX5011.
3M and Solberg exit PFOS-based AFFF agents market.
2001
FFFC (Fire Fighting Foam Coalition) is formed to represent the firefighting foam industry's interests on all issues related to the environmental acceptability of AFFFs.
2002
DuPont acquires Atofina's fluorotelomer surfactant business, including C6
fluorosurfactants.
....................
2003
Chemguard acquires Ciba Specialty Chemicals' Lodyne fluorosurfactant business.
2006
EPA announces the 2010/2015 PFOA Voluntary Stewardship Program.
2011 2014
Tyco acquires Chemguard.
Dynax phases out its C5/C7/C9-based fluorosurfactant, and its only C8-fluorotelomer surfactant (DX2200) All VSP Fluorotelomer manufacturers exit long chain production by year end DuPont spins out Fluoroproducts Business into Chemours
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US EPA PFOA Voluntary Stewardship Program (VSP) 2010/2015
Started in 2006 with 8 fluorochemical manufacturers By the end of 2010, 95% elimination...products & plants By the end of 2015, "work towards the total elimination...
VSP fluorochemical manufacturers ended production of long-chain chemicals (>C8) during or before 2015
In response, most foam manufacturers have transitioned to the use of pure short-chain (C6) fluorosurfactants in Class B foams
Environmental authorities consider perfluorinated chemicals containing less than eight carbons to have a lower potential for toxicity and bioaccumulation
- Short Chains such as C6 Fluorotelomers have regulatory approvals in many global jurisdictions
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TSCA Reform & Impact PMN Process, Innovation & Impact Health Advisory on PFOS and PFOA
- Level: 70 ppt - Additivity: sum of PFOS & PFOA!! - Derivation - Implications - Contrast to Australia's enHealth June 2016
Recommendations: PFOA - 5 ppb and PFOS - 0.5 ppb and - Health C anada's 200 ppt MAC for PFOA
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Draft policy (now Final) on management of fire fighting
foam published by the Queensland Department of
Environment and Heritage Protection (DEHP)
aRestric use of fluorinated foams
Perm
use of fluorine free alternatives
GQouveeernnsmlaenndt
1st draft 2nd draft 3rd draft - Final
December 2013 December 2014 None: 7 July 2016- Final!!**
**Significant Objections raised by FPAA
* by requiring "complete" containment of all discharges and disposal as a regulated waste and justification of C6 Agent usage vs FF
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F/MMgmwinm F r f * r *mMf-i 9ff UM Kwp#r #m mmmmmmimwCSr^ mm mm 1TiM.izfrrlli mJV 'JPrsirrMWBf mm mmm "'m
Most foam manufacturers have developed fluorine-free (FF) foams that provide an alternative to fluorinated agents in some applications
Do not have fire performance across all fuels and in all operational circumstances equal to fluorinated products
2011 paper by Naval Research Labs showed that AFFF agents extinguished gasoline and heptane fires about 70-80% faster than FF
2016 ACS presentation by NRL showed performance of an AFFF to be superior to a FF product:
- Extinguishment: AFFF = 18 sec, FF = 40 sec - Foam Degradation: FF = 1-2 min, AFFF = 35 min
US00002045
F/MMgmwinm F r f * r *mMf-i 9ff UM Kw p#r #m mm mm mm imwCSr^ mm mm T1iM.izfrrlli mJV 'JPrs rirMWBf mm mm m "'m
Fluorine-free foams are inherently oleophilic (fuel attractive) In the absence of oleophobic (fuel-repelling) fluorosurfactants, fluorine-free
foam can easily pick up fuel and the contaminated foam degrades quickly and becomes flammable This fuel contamination problem compromises the fire performance and severely limits the application of fluorine-free foams
Source'. "Flammability & Degradation of Fuel - contaminated Fluorine Free Foams by Chang Jho, International Fire Fighter, 41, Issue 36 - November, 2012
US00002046
Strategic Environmental Research and Development Program Project Proposal 29 Oct 2015
- WPSON 17-01 Fluorine Free Aqueous Film Forming Foam
Proposal Reviews Completed Spring 2016 - Administered by Noblis
Project focused on Performance & Compatibility, EF&E and Toxicology including both ST and LT Research
US00002047
Groundwater and soil studies from fire training areas show multiple releases over many years results in long-term contamination
Major issue at some military bases & some airports
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Source'. "What is Groundwater?" by The Groundwater Foundation, 2016
Any facility where uncontrolled discharges of foam have taken place could have groundwater and soil contamination
Growing concerns in US, Europe, Australia, Canada
US00002048
3M or other PFOS-based foams contain and/or degrade into: - PFOS, PFHxS (C6 homologue of PFOS) - PFOA, PFHxA (C6 homologue of PFOA)
Fluorotelomer-based foams contain and/or degrade into : - 6:2 Fluorotelomer Sulfonate (6:2 FtS), 8:2 FtS - PFHxA, PFOA, resp. (minor breakdown products) - Do not contain or breakdown to PFOS or PFHxS - Misconception to refer to fluorotelomer-based foams as "PFOA foams" and 6:2 FtS is not THPFOS!! - Not made with PFOA; PFOA is not an ingredient in the foam; only contain trace quantities of PFOA as an inadvertent byproduct of the fluorotelomer manufacturing process
US00002049
The vast majority of foam discharges result from the use of foam for training or testing of systems and equipment
FFFC has developed best practice guidance that focuses on using alternative fluids and methods for testing and non-fluorosurfactant foams for training
Also contains detailed guidance on containing and treating foam discharges
Included as additions to NFPA 11, Appendix F
_____________ US00002050
Use fluorinated Class B foams only in situations that present a significant flammable liquid hazard
Before deciding to use fluorinated Class B foam for a specific hazard, investigate whether other non-fluorinated techniques can achieve the required extinguishment and burnback resistance
Be aware of the shortfalls of these alternative methods including no film formation, potential for longer extinguishments and reduced after-fire protection
US00002051
Use training foams that do not contain fluorosurfactants for training and testing purposes
Provide for containment, treatment, and proper disposal of foam solution - do not release directly to the environment
Develop firewater runoff collection plans if not already in place Plan system testing so as to properly contain and dispose of foam
solution effluent generated by the tests
With a live fire there are an unlimited number of circumstances, therefore, any and all actions should consider fire fighter and public safety first and in some cases property protection
Develop plans for dealing with unplanned releases of foam concentrate or foam solution so as to minimize the environmental impact
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Willow Grove - Horsham DuPont/Chemours AUS Senate & QLD DEHP New York VT NH CA AL MN US EPA HA & TSCA Reform EU Regs New York Times Air Force Solicitation Number:
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Regulatory agencies in Canada, Europe, and the United States have proposed regulations on the use of long-chain perfluorinated chemicals Emerging Issues at forefront of conversations The science debate has been reframed: The Fluorochemistry P's Foam legacy contamination issues are likely to be a growing concern Fluorinated fire fighting foams are the most effective agents currently available to fight flammable liquid fires (Class B) Fluorosurfactants provide exceptional extinguishing capability, but also an additional environmental challenge - persistence & mobility Environmental impact is being reduced further with the transition to short-chain (C6) fluorosurfactants Industry is promoting use of best practices to reduce environmental impact of foam
US00002054
Stephen Korzeniow ski shkorzo@ gm aiI.com
BeachEdge C onsulting, LLC
w w w .beachedgeconsuIting.com
Phone: 610-316-8205
US00002055
US00002056
US Environmental Protection Agency (EPA) has proposed a Significant New Use Rule (SNUR) on long-chain perfluoroalkyl chemicals (LCPFACs)
SNUR is intended to provide a regulatory backstop to the US EPA 2010/2015 PFOA Stewardship Program
As proposed, the SNUR would be expected to have minimal impact on the production and use of fire fighting foams
Prohibits
manufacture and import of LCPFACs for new uses and existing uses that are not ongoing
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sale and use of LCPFACs
............................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................. M m L *
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F(CF2)6CH2CH2S 0 2CI
I
6:2 Fluorotelomer Sulfonyl Chloride (6:2 FTSCI)
F(CF2)6CH2CH2S02R AFFF Surfactant Products
biodegradation
F(CF2)6CH2CH2S 0 3-
6:2 Fluorotelomer Sulfonate (6:2 FTSAor 6:2 FTS) 6:2 FTS * THPFOS
biodegradation
6:2 biodegradation pathways
US00002058
It has been determined based on groundwater and soil monitoring studies that the 6:2 fluorotelomer sulfonate (6:2 FtS) is likely the primary breakdown product of the C6 fluorosurfactants contained in telomer-based AFFF - C6F13CH2CH2S 0 3'
Broad range of existing data indicate that 6:2 FtS is not similar to PFOS in either its physical or toxicological properties
- 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
US00002059
Telomer-based foam products may contain trace levels of perfluorohexanoic acid (PFHxA), which is not being addressed by the EPA stewardship program
Telomer-based foams (C6 chemistry) may break down in the environment to PFHxA - research continues
Extensive testing has provided a favorable toxicology profile for PFHxA
- Low aquatic toxicity - Low acute oral toxicity - Not damaging to DNA, not genotoxic or mutagenic - Not a selective developmental or reproductive toxicant - Low biopersistence and not bioaccumulative
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