The shiftto C6 in Firefighting foams and itsimplications ......Jul 03, 2015  · Fire fighting foams...

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