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COOPERATIVE RESEARCH CENTRE FOR CONTAMINATION ASSESSMENT
AND REMEDIATION OF THE ENVIRONMENT
Introduction to firefighting
foams and Per- and poly-
fluorinated alkyl substances
(PFAS) contamination in
environmental media
Prof Ravi Naidu
CEO & Managing Director, CRC CARE
Thursday, 22 February 2018
Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, Callaghan
NSW 2308
Global Centre for Environmental Remediation (GCER), University of Newcastle, NSW
OUTLINE
• Background
– History
– CRC CARE
• Firefighting chemicals
– Introduction
– Types of foams
• Fluorinated
• Fluorine free foams
• Performance of foams
• Commonly used foams in Australia
• PFAS contamination in environmental media
• Environmental impact
• Q & A
• Acknowledgements
OUTLINE OF PRESENTATION 1
CRC CARE
• is a partnership of industry, government
and research organisations
• is a global centre for research and
utilisation of contamination assessment
and remediation technologies
• is developing innovative ways to
remediate and prevent contamination of
soil, water & air
• has key nodes in Australia and China
Headquarters: University of Newcastle
BACKGROUND-CRC CARE
CRC CARE PARTICIPANTS (29)
Site owners/
industry
Government Research providers Service providers
INTRODUCTION
• Is a suppression medium for effectiveness in preventing, extinguishing or
controlling fires involving flammable materials and liquids to save lives and
minimise property damage
- used in fixed and portable fire extinguishing systems as well as fire brigade apparatus
- is produced by mixing foam concentrate with water to produce foam solution
FIRE FIGHTING CHEMICALS -INTRODUCTION
Firefighting chemicals
AFFF may be used to prevent or extinguish fires involving
predominantly Class B fires ONLY
FIREFIGHTING FOAM - FIRE CLASS
FIRE FIGHTING CHEMICALS -INTRODUCTION
• Class A fires – where fire can be deep seated in the burning material in combustible
carbonaceous materials, such as wood, paper, fabric, plastics and rubber
• Class B fires –where the fire and vapours are on the surface in the flammable and
combustible liquids such as liquid hydrocarbon fuels and polar solvents
FIREFIGHTING FOAM APPLICATION
Firefighting foam solution can either be
applied:
• Non-aspirated (through water nozzles, sprinklers
or deluge nozzles)
• Aspirated (when the foam solution is mixed with
air through dedicated foam making devices
including foam branchpipe, top pourer, foam
cannon, foam sprinkler, medium expansion
pourer or high expansion generators).
• NB Check the foam being selected is suitable for
the application method in use.FIRE FIGHTING CHEMICALS-INTRODUCTION
FIRE-FIGHTING CHEMICALS- PFAS
• PFAS chemicals are used in fire
foam products because of their
ability to :
FIRE FIGHTING CHEMICALS-INTRODUCTION
• Fuel repellency - sheds fuel
from the bubble permitting
forceful application to be highly
effective
• faster foam spreading rate than
is possible using only
hydrocarbon-based surfactants
FIRE-FIGHTING CHEMICALS- PFAS
2 important distinctions between PFAS chemicals:
FIRE FIGHTING CHEMICALS-INTRODUCTION
• There are long-chain ≥ C8s including PFOS, PFHxS & PFOA, which are
generally Persistent Bioaccumulative and Toxic (PBT) - no longer being
made (outside China).
• ≤ C6s including PFHxA, PFBA: NICNAS reports that these are P, not B, not
T. Likely constituents of all new fluorinated foams since 2015.
AFFFs are
not equal2 main ways of making PFAS fluorochemicals:
• Electrochemical Fluorination Process (ECF) - breaks down to PFOS, PFOA
& PFHxS - from 3M foams ceased production 2002/3. Still made in China.
• Fluorotelomer Process (FT) - All other fluorochemical and foam
manufacturers - long-chains can break down to PFOA.
TYPES OF FIREFIGHTING FOAM
Firefighting foams can be distinguished
into two broad categories:
• Foams which contain fluorinated surfactants;
(both legacy long-chain C8s and more
environmentally benign short-chain C6s ), and
• Foams which are fluorine free.
However there are also individual foam types
within these two broad categories.
FIRE FIGHTING CHEMICALS-TYPES
FLUORINATED FOAMS
Commonly used firefighting foam types are known by the
following terms
• AFFF—aqueous film-forming foam (3M Lightwater™ brands breakdown to
PFOS/PFHxS, all pre-2016 brands could breakdown to PFOA)
• AR-AFFF—alcohol-resistant aqueous film-forming foam (3M Lightwater™ brands
breakdown to PFOS/PFHxS, all pre-2016 brands could breakdown to PFOA)
• FFFP—film forming fluoroprotein (pre-2016 products could breakdown to PFOA)
• AR-FFFP—alcohol-resistant film-forming fluoroprotein (pre-2016 products could
breakdown to PFOA)
• FP— fluoroprotein foam (pre-2016 products could breakdown to PFOA)
• Short-chain C6 versions of above breakdown to neither PFOS nor PFOA
FIRE FIGHTING CHEMICALS-FLUORINATED
FIREFIGHTING CHEMICALS
Aqueous film-forming foam (AFFF):
• C6 still widely used for fire-fighting by the
military, airports, industry and municipal fire
departments
• complex mixtures of fluorocarbon surfactants,
hydrocarbon surfactants, and solvents
designed to spontaneously spread over
hydrocarbon-fuel fires to extinguish flames and
to prevent re-ignition
• “Limited knowledge on the chemistry of legacy
AFFF beyond that it is a complex mixture of
long-chain C8 fluorochemicals and surfactants
that results in the generation of Persistent,
Bioaccumulative and Toxic (PBT)
fluorochemicals from partially fluorinated
precursors, which can break down to PFOS &
PFOA”
FIRE FIGHTING CHEMICALS-FLUORINATED FOAMS
Persistent in the
environment;
Long-chain C8s
known to bio-
accumulate in
the food chain
FIREFIGHTING CHEMICALS
FFFP—film forming fluoroprotein
• is a natural protein based alternative Film-
Forming FluoroProtein (FFFP) fire fighting
foam concentrate to AFFF, for
extinguishing and securing flammable
hydrocarbon liquid fires.
Environment
• FFFP is readily biodegradable and
virtually non-toxic to aquatic organisms.
It is based on a natural protein foaming
agent and contains no harmful synthetic
detergent or glycol ether, but does have
persistent fluorochemicals - the long-chain
versions could break down to PFOA.
FIRE FIGHTING CHEMICALS-FLUORINATED FOAMS-
FIREFIGHTING CHEMICALS
AR-AFFF—alcohol-resistant aqueous film-forming foam
• used in high risk situations where hydrocarbons (such as crude oil, gasoline, diesel fuel, aviation kerosene) and/or polar solvents (such as alcohols, ketones, esters, and ethers) are stored, processed, or transported.
• Typical applications include hydrocarbon storage tanks, process areas, warehouses, road/rail loading racks, power stations, marine terminals, and offshore platforms.
Environment
• readily biodegradable and low toxicity to aquatic organisms. It is based on a synthetic detergent foaming agent and contains long or short-chain fluorchemicals.
FIRE FIGHTING CHEMICALS-FLUORINATED FOAM
FIREFIGHTING CHEMICALS
AR-FFFP—alcohol-resistant film-forming
fluoroprotein
• is a natural protein based alternative Alcohol
Resistant Film-Forming FluoroProtein (AR-FFFP)
fire fighting foam concentrate to AR-AFFF for
extinguishing and securing flammable hydrocarbon
and polar solvent liquid fires.
Environment
• readily biodegradable and virtually non-toxic to
aquatic organisms. It is based on a natural protein
foaming agent and contains no harmful synthetic
detergent or glycol ether, but does have persistent
fluorochemicals - the long-chain versions could
break down to PFOA.
FIRE FIGHTING CHEMICALS-FLUORINATED FOAM
FIREFIGHTING CHEMICALS
Fluoro protein foam (FP):
• Fluoro Protein (FP) fire fighting foam
concentrate for extinguishing and securing
flammable hydrocarbon liquid fires,
especially tank fires and bunded areas.
Environment
• FP is biodegradable and virtually non-
toxic to aquatic organisms. It is based on
a natural protein foaming agent and
contains no harmful synthetic detergent or
glycol ether solvents, but does have
persistent fluorochemicals - the long-chain
versions could break down to PFOA.
FIRE FIGHTING FOAM-FLUORINATED FOAM
FIREFIGHTING CHEMICALS
High expansion foam (HI-EX):
• produces large-volumes of high expansion
foam for use in total flooding applications,
marine fire fighting and Liquefied Natural
Gas (LNG) applications
Environment
• Fluorine Free, HI-EX is 100%
biodegradable (but can be toxic?) to
aquatic organisms in concentrated form
and even at normal use strength.
FIRE FIGHTING CHEMICALS –FLUORINE FREE FOAM
FLUORINE FREE FOAMS
FIREFIGHTING CHEMICALS-FLUORINE FREE FOAM
Fluorine-free foam (FF or F3):
• FF concentrate for extinguishing and securing
flammable hydrocarbon liquid fires. Most
effective on smaller fires and for training.
• Environment
Fluorinefree foam technology has now become
a reality (varying levels of uptake based on
performance)
FLUORINE FREE FOAMS
FIREFIGHTING CHEMICALS-FLUORINE FREE FOAMS
2 Examples fire test results for FF foams
Comparative testing in Spain 2016 (table
above) at 2.5L/min/m2 showed:
F3 60% slower control on Gasoline
F3 50% slower control on Jet A1
ENVIRONMENTAL IMPACT OF FLUORINE FREE
FOAMS
• Most fluorine-free foams have been shown to be an order
of magnitude higher in acute aquatic toxicity than
fluorotelomer-based foams where hydrocarbon surfactants
have been used to replace fluorosurfactants.
• Past testing has demonstrated that fluorine-free foams do
not often show equivalent fire performance to C6
alternatives
FLUORINATED VS FLUORINE FREE FOAM
• C6 AFFF agents extinguished all gasoline and heptane
fires in less than 30 seconds, the time required to pass
the United States military specification (milspec)
Vs
• The fluorine-free foam was unable to extinguish any
gasoline or heptane (milspec) fire in less than 30seconds.
NB US Airforce has transitioned to C6 AFFFs (not F3s).
PERFORMANCE OF FOAMS
PERFORMANCE OF FOAMS
PERFORMANCE OF FOAMS
Table 1 : Fire Out Times (seconds)
Foam Type Heptane Gasoline MCH Isooctane
AFFF(3%) 25 21 19,20 32,33
AFFF(6%) 23,28 22 22,23 32,33
Fluorine-free(6%) 43 35,41 33,46 29,30
Table 2 : Spray Extinction Fire Out Times(minutes)
Foam Type Heptane Gasoline Kerosene Jet A-1
AFFF(1%) 1:03 0:38 0:22
AR-AFFF 1x3 2:11 1:25 1:25
Fluorine-free (1%) 2:14 3:36 3:12
Fluorine-free (1%) 2:21 2:21 3:21
Fluorine-free (3%) None None 1:00
For a fire safety engineer, the selected foam should be able to extinguish the
fire in a shortest time possible to save lives and property for its fire size,
effectively, efficiently and reliably to save lives and reduce firewater runoff
• Foam agents must meet the milspec on the US Department of Defense qualified
products database (QPD) for military applications .
• The FAA requires all US airports to carry AFFF agents that meet the milspec and are
listed on the QPD (ie C6 AFFF formulations)
• Australia Department of Defence require AFFF agents that meet the US milspec
COMMONLY USED FOAMS IN AUSTRALIA
COMMONLY USED FOAMS IN AUSTRALIA
Fire
Firefighting
Foam
Class - type
of fire
Contains
PFAS
Contains Other
Hydrocarbon
surfactants
Training
UseNormal Use
Emergency
use
AFFF
3%/6%/1%
Class B Yes Yes No Emergency
Testing
Calibration
Military, Air
Hangars, MHFs,
Mining,
Offshore,
Industrial etc.
F3
3%,6%
AR-F3
3x3, 3x6
Class B No Yes Yes Emergency
Training
Testing
Calibration
Fire Brigades,
Ports, airports,
some industrials
mining
FP
3%
Class B Yes No No Emergency
Testing
Calibration
Oil industry &
storage Tank
fires
Government is working to ratify the 2009 Stockholm Convention amendment and ban
PFOS from use in Australia (mostly now held in reserve waiting disposal)
COMMONLY USED FOAMS IN AUSTRALIA
Fire
Firefighting
Foam
Class -
type of fire
Contains
PFAS
Contains
Other
Hydrocarbon
surfactants
Training
UseNormal Use
Emergency
use
AR-AFFF
1x3, 3x3, 3x6
Class B Yes Yes Some
Firefighter
training
Emergency
Testing
Calibration
Oil &
Petrochem
MHFs,
Brigades
AR-FFFP
3x3, 3x6
Class B Yes No Some
Firefighter
training
Emergency
Testing
Calibration
Oil &
Petrochem,
MHFs,
Brigades
AFFF/AR-AFFF
3M Lightwater
Contains
PFOS
PFOA
Yes
DO NOT USE
Class A Foams Class A No Yes Yes Emergency
Test/Calibration
Bushfires
COMMONLY USED FOAMS IN AUSTRALIA
Most fluorinated foam users are transitioning away from C8s, to either:
C6 or F3 agents
FOAM SELECTION AND USE
Effectiveness of a type of firefighting foam in achieving the
goals MUST be a prime consideration in its selection and use.
Selection criteria:
(a) Firefighting performance
(b) Life safety
(c) Physical properties and suitability for use on known hazards
(d) Compatibility with system design and approvals
(e) Reduced environmental impacts & firewater runoff
PERFORMANCE OF FOAMS
Instant risk
to people
properties,
etc.
Long term
environmental
risks
Fluorine
foams
Fluorine
Free
foams
Acute
toxicity,
runoff,
reliability
Suitability? Performance? Environmental impact? Etc…
ENVIROMENTAL IMPACT
• Foams, chemicals, smoke and runoff have acute and chronic
impacts on biodata, soils and waterways
ENVIRONMENTAL IMPACT
“No substance is a
poison by itself. It is the
dose that makes
a substance a poison...”
Paracelsus
(1493-1541)
Risk = Toxicity + Exposure
Reduce exposure!!
Reduce use &
runoff !!
Case #3: (Reuters) - DuPont and
Chemours Co have agreed in 2016 to pay
$671 million in cash to settle thousands of
lawsuits involving a leak of a toxic chemical
used to make Teflon (mostly legacy PFOA)
Case #1: Most of the training sites at ~49,000
of the world’s airports, including ~450 ones
in Australia, have a high accumulation of
PFASs that often escape into environment.
(mostly legacy PFOS)
Case #2: (ABC) - The NSW environmental
watchdog has started a statewide
investigation into the historical use of
firefighting foam that is at the centre of water
contamination near Newcastle. (mostly legacy
PFOS)
PFAS CONTAMINATION
PFAS CONTAMINATION
Case #5: Due to Japan earthquake in
2011, 0.8-1 tons of PFOS + 4.8-5.1 tons of
PFOA were discharged to Pacific Ocean.
Case #6: PFASs used in soil- and stain-
resistant coatings on upholstery, carpets,
leather, floor waxes, polishes, and in fire-
fighting foams were potentially released
during the collapse of the WTC in 2001.
(mostly legacy PFOS/PFOA)
Case #4: Brisbane Airport’s owners are
suing Airservices Australia over
contamination caused by the decades-
long use of toxic foam by aviation
firefighters. (mostly legacy PFOS/PFOA)
SUMMARY
Foams can pose a range of hazards to the environment when
released during activities such as training, maintenance, testing,
incident response, fire, waste disposal.
Various types of C6 fluorine and fluorine free foams are currently available and
these need to be investigated for their life safety & fire performance, suitability,
reliability, efficiency, toxicity, environmental impact, etc.
Some fluorine free foams could be magnitude higher toxicity than their counter
parts, and require more usage, which would require further investigation
Varying information is available in the public domain on the different
environmental and fire firefighting performances of C6 fluorinated and fluorine-
free foams
The selection of foams should be based on balanced consideration of life safety,
effectiveness, reliability, short term and long term risks
When considering risks, the use/exposure assessment should be emphasised
PFAS CONTAMINATION
RISK AND REMEDIATION
• CRC CARE and the UoN provides support towards
assessment of potential risk from exposure to fire fighting
foams
• Refer to CRC CARE Guidance document on PFAS
(www.crccare.com)
• Fire Protection Association Australia, IB-06 Info Bulletin
http://www.fpaa.com.au/technical/technical-
documents/information-bulletins/ib-06-v11-selection-and-use-
of-firefighting-foams.aspx
• Remediation: presentations today and also risk based
approach- contact: admin@crccare.com
Acknowledgements
Thank you for your attention!
Dr Joytishna Jit;
Dr Mike Wilson
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