the shiftto c6 in firefighting foams and itsimplications ......jul 03, 2015 · fire fighting foams...
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The shift to C6 in Fire fighting foamsand its implications
Anna KärrmanMTM Research Centre
Sweden2015-07-17
Past usage of fluorinated foams
• AFFF; Aqueous film forming foams• AFFF-AR; Alcohol resistent foams• Complex mixtures for extinguish fires involving highly
flammable liquids• ECF-products (PFOS-based) introduced mid 80s.• Product shift after 3M phase-out in 2002 to telomer-
based products
• (ECF production of PFOS and PFHxS for AFFF applications still ongoing)
2015-07-17
∑PFAA7 : PFBS
PFHxS
PFOS
PFPeA
PFHxA
PFHpA
PFOA
Environmental contamination
• Contaminated grounds and water, mainly from military excercise grounds
• Ground water contamination
•
• 3.6 million Swedes affected
Response from the National Food Agency • Limit of action for ∑ 7 PFAAs likely found in water• TDI (PFOS) for infants, 10% from water/day• Cumulative effect* for 7 PFAAs is presumed• Limit of action 90 ng/L
2015-07-17 National Food Agency 2014*Assuming similar effect for all 7 PFAAs
Regulatory actions
EU • Foams with >0.001 w% PFOS banned after June 2011
National (Sweden)• Gouvernment focus and action plan for PFASs 2015-2016 • 2015 inventory of current usage and possible alternatives
2015-07-17
Textiles and leathersPaper, food packagingFire fighting foamsCosmeticsHousehold productsImpregnation for fabricsPaints
Polish and cleainingNon-stick productsSki-waxChrom plating industryHydraulic oil air craftsOthers
Present
Review of the fire agents on the Swedish market wasconducted in 2014
Selection of fire agents for analysis and evaluation:• chemical analysis• acute ecotox-effects• formation of by-products during useage
2015-07-17
ResultsOut of the 10 products selected for chemical analysis, only foams
for fire in liquids (B-class foams) contained PFAS
• Foams for fibrous fires
• For liquid (petrol, alcohols) fires
• Additive agents (does not form a foam)
2015-07-17
S
F F
F F
F F
FF
FF
FF
F
O
O
NH N+
OH
CH3 CH3O
Results
• 6:2 fluorotelomers in all class B foams•
• Only traces of longer chain PFAAs• Environmental degradation to perfluorinated alkyl acids is
expected
2015-07-17
F
F
F
F
F
F
F
F
F
F
F
OH
O
6:2 FTSPerfluorinated acids C4-C6
PFAA profile in foams
2015-07-17
Two samples (green and blue) from new containers.
6:2 FTS and PFHxA is relatedto one of the main ingredients; 6:2 fluorotelomer sulfonamide amine
0
500
1000
1500
2000
2500
PFBA
PFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
PFDoDA
PFTrDA
PFTDA
PFHxDA
PFOcDA
PFBuS
PFHxS
PFOS
PFDS
6:2 FTS
ARC Miljö 1 ARC Miljö 3
PFAA profile in foams
2015-07-17
0
500
1000
1500
2000
2500
PFBA
PFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
PFDoDA
PFTrDA
PFTDA
PFHxDA
PFOcDA
PFBuS
PFHxS
PFOS
PFDS
6:2 FTS
ARC Miljö 1 ARC Miljö 2 ARC Miljö 3
One sample (red) from a rescueservice station
PFOS and PFHxScontamination from previouslyused foams
Biotransformation to persistent PFAAs– an environmental problem?
2015-07-17
0
500
1000
1500
2000
2500
PFBAPFPeA
PFHxA
PFHpA
PFOA
PFNA
PFDA
PFUnDA
PFDoDAPFTrDA
PFTDA
PFHxDA
PFOcDA
PFBuS
PFHxS
PFOS
PFDS
6:2 FTS
ARC Miljö 1 ARC Miljö 2 ARC Miljö 3
Red = Persistent, Bioaccumulating, [Toxic]
Green = Persistent, [Toxic]
Fire, January 3rd 2015
2015-07-17
Two different foam products used, 20L concentrate of each. One contain PFASs
PFASs in the foam used
2015-07-17
S
O
O
OHNHS
CH3 CH3OF F
F F
F F
FF
FF
FF
F
0
1000
2000
3000
4000
5000
6000
7000
8000
PFBS PFHxS 6:2 FTS PFBA PFPeA PFHxA PFHpA PFOA
ug
/kg
Supplier End-user14000
Non-target analysis• 6:2 FTSAS
(fluorotelomermercapto-alkylamido sulfonate)
Target analysis • 6:2 FTS• C6-C4 PFCA
January 4th. Deep drilled wells in the area are contaminated
2015-07-17
0
10
20
30
40
50
60
70
80
90
PFBS PFHxS PFPeA PFHxA PFHpA PFOA 6:2 FTS
ng
/L
Jan 6
Jan Feb March June
∑PFAA7
ng/L117
0
200
400
600
800
1000
1200
1400
1600
PFBS PFHxS PFPeA PFHxA PFHpA PFOA 6:2 FTS
ng
/L
Jan 5 Jan 6 Feb 11 March 25 June 11
6500
Analysis of the drinking water
2015-07-17
Jan Feb March June
∑PFAA7
ng/L117 2176 151 900
Ongoing national regulatory actions
Different scenarios currently under discussion (KEMI*):• Foams with PFASs prohibited with exceptions for specific
applications• Approval needed before all usage• Report must be filed after all usage• Others:
•••••
2015-07-17 *KEMI (Swedish Chemical Agency): Jenny Ivarsson, Bert-Ove Lund
Acknowledgment:Project group: Jessika Hagberg, Filip Bjurlid, Niklas
Ricklund, Maria Larsson, Jordan Stubleski
2015-07-17