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