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The 3F basics

The 3F concept is simple and is based on the three fundamental aspects to ensure safe fire extinction.

The answer to replace these chemical components lies in the combination of surfactants and polymers on a natural basis and the synergistic combination of their properties allowing a complete range of foams to be used.

FOAMS

We propose a wide range of foams ensuring that the user has the best solution for his risk.

EQUIPMENT

We provide equipment to apply foam onto the fire in the safest, most efficient and economical manner.

ENVIRONMENT

An environmentally friendly complete solution that, beyond overall performance and efficiency, will eliminate the environmental damage caused by foams.

SMART FOAM®
A range of environmentally friendly foams

3F is committed to the path of fluorine-free products with its class A additives and class B multi-purpose foams. 3F innovates and launches its SMART FOAM -SF range of solvent-free foams as a preview on the market.

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A global network

The 3F network around the world

3F is a company run by experienced people who have demonstrated their knowledge in firefighting over the last thirty years. With offices in England, Singapore and Panama, our company is able to respond quickly and efficiently to the demands of our customers all over the world.

Togo

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Benin

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Niger

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Mauritania

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Mali

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Burkina Faso

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Madagascar

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Angola

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

New Caledonia

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Luxembourg

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Belgium

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Croatia

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Hungary

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Romania

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

New Zealand

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Salvador

3F AMERICAS Inc.

Xiomara Escalante

ventas@3famericas.com

+507 6494 5421

Belize

3F AMERICAS Inc.

Xiomara Escalante

ventas@3famericas.com

+507 6494 5421

Canada

3F AMERICAS Inc.

Thierry Bluteau

export@3famericas.com

+33 761 461 665

United Arab Emirates

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Cuba

3F AMERICAS Inc.

Xiomara Escalante

ventas@3famericas.com

+507 6494 5421

Honduras

3F AMERICAS Inc.

Xiomara Escalante

ventas@3famericas.com

+507 6494 5421

Nicaragua

3F AMERICAS Inc.

Xiomara Escalante

ventas@3famericas.com

+507 6494 5421

Dominican Republic

3F AMERICAS Inc.

Xiomara Escalante

ventas@3famericas.com

+507 6494 5421

Costa Rica

3F AMERICAS Inc.

Xiomara Escalante

ventas@3famericas.com

+507 6494 5421

Guatemala

3F AMERICAS Inc.

Xiomara Escalante

ventas@3famericas.com

+507 6494 5421

Mexico

3F AMERICAS Inc.

Armando Merino

amerino@3famericas.com

+52 442 336 0675

Bolivia

3F AMERICAS Inc.

Pablo Rojas

projas@3famericas.com

+593 99 99 600 92

Colombia

3F AMERICAS Inc.

Pablo Rojas

projas@3famericas.com

+593 99 99 600 92

Peru

3F AMERICAS Inc.

Pablo Rojas

projas@3famericas.com

+593 99 99 600 92

Ecuador

3F AMERICAS Inc.

Pablo Rojas

projas@3famericas.com

+593 99 99 600 92

Chile

3F AMERICAS Inc.

Pablo Rojas

projas@3famericas.com

+593 99 99 600 92

Panama

3F AMERICAS Inc.

Thierry Bluteau

export@3famericas.com

+33 761 461 665

Argentina

Melisam Fire Group

Melisam Fire Group

info@melisam.com

5411 4766-6100

Uruguay

3F AMERICAS Inc.

Thierry Bluteau

export@3famericas.com

+33 761 461 665

Venezuela

3F AMERICAS Inc.

Thierry Bluteau

export@3famericas.com

+33 761 461 665

Brazil

3F AMERICAS Inc.

Thierry Bluteau

export@3famericas.com

+33 761 461 665

Australia

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Oman

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Iraq

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

India

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

China

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Pakistan

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

South Korea

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Japan

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Brunei

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Laos

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Cambodia

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Taiwan

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Philippines

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Thailand

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Vietnam

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Indonesia

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Malaysia

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Singapore

3F ASIA

Kenneth Loh

kenneth@3fffasia.com

+65 9738 3218

Sudan

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Egypt

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Kenya

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

South Africa

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Mauritius

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Congo BZ

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Gabon

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Ghana

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Cameroun

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Ivory Coast

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Senegal

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Libya

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Tunisia

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Algeria

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Morocco

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Italy

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Switzerland

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Portugal

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Spain

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

France

3FFF Ltd

Thierry Bluteau

export@3fff.co.uk

+33 761 461 665

Malta

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Cyprus

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Turkey

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Greece

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Netherlands

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Austria

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Germany

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Poland

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Lithuania

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Latvia

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Estonia

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Finland

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Sweden

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Norway

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Denmark

3FFF Ltd

Gary McDowall

sales@3fff.co.uk

+44 1536 202 919 / +44 7801 850 011

Ireland

ABC McIntosh Ltd

Becky McDowall

becky@abcmacintosh.com

+44 1536 260 333

United Kingdom

ABC McIntosh Ltd

Becky McDowall

becky@abcmacintosh.com

+44 1536 260 333

News

From AFFF to F3 : Chemistry – Part 2

In this part we deal with the chemistry involved in formulating Class A foams for carbonaceous fuels, and legacy Class B AFFF foams based on PFOS chemistry for liquid hydrocarbon and polar solvent fires.

In Part 1 of this series of articles we saw that AFFF firefighting foams contain various perfluoroalkyl substances (PFAS); however, firefighting foam is only one of many applications.
PFAS have been used for decades in more than 200 other industrial and domestic applications, such as food packaging, leather and textile treatment, carpet and clothing anti-stain protection, detergents, water-proofing and oil-proofing, paints and varnishes, printing inks, chromium plating, outdoor and protective clothing (PPE) for the emergency services and military. These perfluorinated substances are widely used as they offer a combination of unique properties, including the ability to repel water (hydrophobicity), the ability to repel oils (oleophobicity), the ability to reduce the surface tension of aqueous solutions to less than 20 dyne/cm and with it acting as detergents, emulsifiers, wetting agents, and dispersants.

The OECD (2021) has recently clarified the definition of what constitutes a PFAS, whilst acknowledging that given by Buck et al (2011), as follows:

“PFASs are defined as fluorinated substances that contain at least one fully fluorinated methyl or methylene carbon atom (without any H/Cl/Br/I atom attached to it), i.e. with a few noted exceptions, any chemical with at least a perfluorinated methyl group (–CF3) or a perfluorinated methylene group (–CF2–) is a PFAS.”

More than 800 products currently available in the marketplace have been identified, but the true list of PFAS used in commerce and industry is likely to be 10,000 or more; the UN Stockholm Convention has listed 4,700 substances related to PFOA alone. PFAS started to be manufactured in large quantities in the early 50’s. All of them are anthropogenic created by humans using chemical synthesis. They do not exist naturally. Their extremely stable and chemically resistant perfluorinated end-products of breakdown in the environment have long been identified as ‘forever chemicals’, for example by scientists and journalists such as Rebecca Renner [“Growing Concern Over Perfluorinated Chemicals” (2001) Environ. Sci. Technol. 35(7) 154A-160A; “The long and the short of perfluorinated replacements” (2006) Environ. Sci. Technol. 40(1) 12-13] or Sharon Lerner writing in the Intercept [“Toxic Chemicals Discovered in Hundreds of Products” Sharon Lerner (The Intercept December 2020)].

It must be stressed that although still commonly and inaccurately referred to as ‘emerging contaminants’, PFAS have truly emerged as contaminants of concern for at least 10 years and should no longer be described as ‘emerging’. On the other hand, the technology of how to deal with PFAS waste is currently still emerging and developing.

Firefighting foams are classified either as Class A suitable for carbonaceous fuels such as wood, paper or vegetation, acting as wetting agents improving the penetration of water into deep seated fires and do not contain fluorosurfactants, only hydrocarbon surfactants; or, on the other hand, Class B foams are specifically formulated for liquid hydrocarbons such as gasoline and polar solvents such as ethanol. Modern Class B foams may either contain fluorsurfactants and be capable of film-formation at the air-fuel interface (AFFF), or completely fluorine-free, F3 foams, specially formulated containing only hydrocarbon surfactants. Interestingly Class B fluorine-free foams (F3) can be used effectively for both Class A and Class B fires unlike AFFF,

Class A foams for carbonaceous fuels

Class A firefighting foams are used extensively worldwide, especially in Australia, America and Southern Europe, for incidents involving carbonaceous fuels, e.g., structural house fires, plastic and tyre waste, as well as grassland and wildland or bush fires. Ted Schaefer then working for
3M Australia in the late 1980s developed one of the first effective Class A foams, “3M Fire-Brake BFFF”, recognised in 2001 by the Australian Academy of Technological Sciences and Engineering as one of the top 100 Australian inventions of the 20th century.
Class A foams behave very differently to fluorosurfactant-containing AFFFs, as they are specifically formulated to penetrate carbonaceous fuel effectively, such as compacted vegetation, paper or wood, using specialised hydrocarbon surfactants, not unrelated to kitchen washing-up liquid. Fluorosurfactant AFFFs, designed for surface application to liquid hydrocarbon or polar solvent fires, are nowhere nearly as efficient at penetrating such deep-seated fires and claims by some in the industry that their AFFF products can be used as dual Class A / Class B foams is frankly misleading.

Mister H: Penetration by Class A                          Mister F: Failure to penetrate by Class B AFFF

(Bluteau 2007)

Class B AFFF foams for liquid hydrocarbons and polar solvents

The first report of an aqueous film-forming foam (AFFF), called LightWater®, by R.L. Tuve et al of the Naval Research Laboratory and the 3M Company March 1964 of a foam capable of vapour suppression and film forming on the surface with low flash point flammable fuels such as gasoline, showed that it was 1200% more effective than standard protein foams under identical conditions.
The compounds tested in foam formulations were in the general class of perfluorosulfonic acid derivatives, some being quaternary salts, others being alcohols, esters, anionic salts of substituted sulfonamido carboxylic acids, etc. All of these water soluble, high molecular weight fluorocarbons shown dramatic surface tension depression of water to below 20 dynes/cm. In general they are insensitive to electrolytes and show surface activity when dissolved in organic solvents.
The first Patent for an AFFF was granted to Richard Tuve and Edwin Jablonski in June 1966 [1], representing a new era in firefighting foams which was to last for the next 30-40 years until the 3M Company Minnesota withdrew from PFOS-based chemistry altogether in May 2000.

Information from the patent literature gives a fascinating insight into the derivatives used in these early AFFFs. Derivatives of perfluorooctane sulfonamide (PFOSA) and perfluorooctane carboxylic acid (PFOA) were used. As reported in the 1966 patent these early formulations include the quaternary ammonium salts of PFOS and PFOA amido derivatives:

C8F17-SO2NH2-(CH3)3N(CH3)3+I-

C7F15-CONH-(CH3)3N(CH3)3+I-

an amphoteric amino betaine derivative of PFOA

C7F15-CONH-(CH2)3–N+(CH3)2-CH2-CH2-COO

and the potassium salt of a PFOS sulphonamide derivative

C8F17SO2N(C2H5)-CH2COOK

The potassium salt of PFOS in the form of surfactant FC-95 was also used in early foams.
Interestingly it was some 50 years later that Barzen-Hanson et al in 2017 [2] from Jennifer Field’s group at Oregon State University identified a vast range of other derivatives, or their breakdown products, involving 40 different classes in legacy AFFFs.

Electrochemical Fluorination (ECF) – the Simons Process

The 3M Company announced in May 2000 that it was phasing out fluorosurfactant production based on PFOS chemistry and withdrawing entirely from the fluorinated AFFF firefighting foam market marking an end to the availability of Light Water™ and Light Water™ ATC™ formulations (3M Company (2000)). Other products using PFOS included ScotchGuard™ stain and water repellent treatments. Production of PFOS by the 3M Company is thought to have ceased entirely around 2002, being replaced by the shorter chain compound PFBS, although PFOS and PFHxS production is thought to have continued in China and India.
Until 2000 PFOS had been manufactured using the Simons electrochemical fluorination (ECF) process (3M Company, 1999; Ignat’ev et al , 2009; Sartori and Ignat’ev, 1998). This process involves replacing the hydrogen atoms of octyl sulfonate using hydrogen fluoride electrolytically in order to generate perfluorooctane sulfonyl fluoride, PFOSF.

C8H17SO3H + HF ==>> C8F17(C=O)F

PFOSF is highly reactive acyl fluoride and is the starting material for preparing PFOS derivataives such as the sulfonamide PFOSA or N-ethyl-PFOSA, for example:

C8F17(C=O)F + C2H5NH2 ==>> C8F17(C=O)-NH-C2H5

 

PFOSF production using electro-chemical fluorination (ECF) was, and remains, an inherently ‘dirty’ process resulting in a wide range of structural isomers, both straight chain and branched with CF-CF3 and C-(CF3)2 side chains, as well as odd and even chain length homologues such as C4 PFBS, C6 PFHxS and C7 PFHpS. As a result, technical grade PFOS was always and continues to be contaminated with a significant percentage of PFHxS. In addition, the perfluoroalkyl chains of both PFOS and PFHxS can form left- or right-handed helices resulting in pseudo-racemates that have been detected in human sera (Wang et al, 2011; Naile et al , 2016; Sasaki et al , 2018). Quoting from the ECHA (13 June 2019) PFHxS restriction proposal:

…Sources indicate that when manufacturing perfluorinated compounds, a mixture of compounds of varying chain- length is usually formed, with typical amounts of PFHxS formed when manufacturing PFOS being between 4 and 14% ( from (BiPRO, 2018) citing (Ren, 2016). These numbers are supported by measurements of PFHxS in commercial PFOS-products, namely 3.5%–9.8% in 3M’s FC-95 (from (BiPRO, 2018) citing 3M (2015) and 11.2 % – 14.2% in three products from China (Jiang et al, 2015). BiPRO also note, however, that the amount of the C6-component may be reducedby purification at different stages of the production line….

The significance of the relatively high levels of the C6 homologue perfluorohexane sulfonic acid, PFHxS, in these AFFF formulations is that PFHxS is more toxic and bioaccumulative than PFOS, has a longer biological half-life in humans, and has also been list in the Annexes of the UN Stockholm Convention for restriction. Unfortunately, some manufacturers especially in Asia have used PFHxS as a ‘regrettable substitution’ for PFOS.

The use of ECF to produce perfluorinated sulfonic and carboxylic acids, such as PFOS and PFOA and their derivatives, has been summarised by Buck et al [2011], as shown below.

source: Buck et al (2011)

To be continued as Part3.

References

Barzen-Hanson, K.A., Roberts, S.C., Choyke, S., Oetjen, K., McAlees, A., Riddell, N., McCrindle, R., Ferguson, P.L., Higgins, C.P., and Field, J.A.. (2017) “Discovery of 40 Classes of Per- and Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater” Environ, Sci. Technol. 51, 2047-2057.

Benskin J.P., De Silva A.O., Martin J.W. (2010) Isomer Profiling of Perfluorinated Substances as a Tool for Source Tracking: A Review of Early Findings and Future Applications. Rev. Environ. Contam. Toxicol.:111-160.

Buck, R.C., Franklin, J., Berger, U., Conder, J.M., Cousins, I.T., de Voogt, P., Jensen, A.A., Kannan, K., Mabury, S.A., and van Leeuwen, S.P.J. (2011)  Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins. Integr. Environ. Assess. Manag. 7(4), 513-541.

Ignat’ev, N.V., Willner, W., and Sartori, P. (2009)  Electrochemical fluorination (Simons process) – A powerful tool for the preparation of new conducting salts, ionic liquids and strong Brǿnsted acids. J. Fluorine Chem. 130(12), 1183-1191.

Naile, J., Garrison, A.W., Avants, J.K., and Washington, J.W. Isomers/Enatiomers of Perfluorcarboxylic Acids: Method Development and Detection in Environmental Samples. Chemosphere 44, 1722-1728.

OECD (2021), Reconciling Terminology of the Universe of Per- and Polyfluoroalkyl Substances:

Recommendations and Practical Guidance, OECD Series on Risk Management, No. 61, OECD

Publishing, Paris.

Sartori, P. and Ignat’ev, N.V. (1988) The actual state of our knowledge about mechanism of electrochemical fluorination in anhydrous hydrogen fluoride. J. Fluorine Chem. 87(2(, 157-162.

Sasaki, T., Egami, A., Yajima, T., Uekusa, H., and Sato, H. (2018) Unusual Molecular and Supramolecular Structures of Chiral Low Molecular Weight Organogelators with Long Perfluoroalkyl Chains. Crystal Growth and Design 18(7) 4200-4205.

Tuve, R.L. amd Jablonksi, E.J. (1966) US 3,258,423 Patent June 28, 1966 “Method Of Extinguishing Liquid Hydrocarbon Fires”, assignors to the United States of America as represented by the Secretary of the Navy. Filed Sept. 4, 1963, Ser. No. 306,665.

Vyas, S.M., Kania-Korwel, I., Lehmler, H.J. (2007) Differences in isomer composition of perfluorooctanoylsulfonyl (PFOS) derivatives. J. Environ. Sci. Health and Toxic Hazard Substance Environ. Eng. 42, 249-255.

Wang,  Y., Beeson, S., Benskin, J.P., De Silva, A.O., Genuis, S.J., and Martin J.W. (2011) Enantiomer Fractions of Chiral Perfluoroctanesulfonate (PFOS) in Human Sera. Environ. Sci. Technol. 45(20) 8907-8914.

Read more

From AFFF to F3 : History – Part 1

Modern chemistry has created many hundreds of thousands of chemical compounds, which we encounter as part of our daily lives. Indeed, it would be very hard to spend a day without being in contact with a class of molecules – perfluoroalkyl substances or PFAS – which have been commercially exploited since the end of WWII over the last 75 years.

Even if we could qualify chemistry as a miracle of science, it is worth knowing that chemistry has been approached by the Egyptian 3000 years BC, and was later on studied by the Ancient Greeks which described the combination of the 5 elements: earth, air, fire, water and ether. This theory was largely accepted for more than 1000 years.

The basis of the modern chemistry, as we now understand it, was established over the last three hundred years. The nature of the atom, the identification of atomic compounds, the first modern synthesis was achieved.

In 1906, Frédéric Henri Moissan (1852-1907), a French chemist working in Paris at the École Supérieure de Pharmacie, isolated for the first-time elemental fluorine gas, F2, a discovery for which he was awarded the Nobel Prize in Chemistry in 1906. Hydrogen fluoride obtained from fluorspar had been identified by the renowned Swedish chemist Karl Wilhelm Scheele some years earlier.

The post war years after WWI In the mid 1930s, were the heyday the German chemical industry, especially as regards new synthetic dyes. Fluorine chemistry started to have a commercial role – a red dye Naphthol AS, used as the official red colour the Nazi flag, and Indanthrene Blue used as a component of ‘Flieger Grau’ or Pilot Grey, the blue-grey colour of Luftwaffe uniforms, both contained a fluorinated methyl group, CF3, which helped prevent fading. Carothers working for DuPont produced the first industrial wholly synthetic fabric, the polymer Nylon. From this point chemists have never stopped to inventing new compounds!

When we think about chemicals, it is important to realise that many, if not most of the synthetic compounds now commercially available are produced by the petrochemical industry. Since the invention of the internal combustion engine, petrol (gasoline) and petroleum products have been become increasingly important around in for many human activities but are associated with a high fire risk.
The nature of this risk highlighted the necessity of addressing these often-catastrophic fires. In the early 40’s, protein foam made from ‘horn and hoof’, a slaughterhouse waste, was developed to control Class B hydrocarbon fires, e.g., those involving oil, gasoline, aircraft fuel and solvents.
In 1949, the 3M Company Minnesota industrialized the Simons electrochemical fluorination (ECF) process for making perfluoro-compounds (PFC) such as perfluorinated amines, carboxylic and sulphonic acids in which the hydrogens of the alkyl carbon chain had been totally replace by fluorine. Joseph Simons had discovered the ECF process whilst working at Pennsylvania State College in the 1930s but was unable to publish his work until after WWII because fluorine chemistry was essential for uranium purification as part of the Manhattan Project.

In 1953 the structure of Scotchgard was accidentally discovered by Patsy Sherman and Sam Smith working for the 3M Company whilst working on a rubber for jet fuel lines. Three years later in 1956, the 3M Company launched Scotchguard on the market. This fabric, textile and leather treatment is based on a PFOS-derivative containing N-ethyl-PFOSA and gives water, oil, and other liquids and stain-protection to the treated fibre.
Interestingly, N-ethyl-PFOSA known as Sulfluramid, was originally developed to kill ants, cockroaches and termites, and is still used to this day as the insecticide sulfluramid against leaf-cutting ants in Brazil. The lithium salt of PFOS was developed to kill wasps and hornets but is highly toxic to honey bees.

PFOS, perfluoro-octane sulphonic acid, and its derivatives subsequently become crucial for the development of Class B aqueous film-forming foams (AFFFs) effective against liquid hydrocarbon and solvent fires.

Figure 1. The structure of PFOS, perfluoro-octane sulphonic acid.

During the 1960s the US Department of the Navy Naval Research Laboratory in collaboration with the 3M Company began developing PFOS-based firefighting foams. A patent for AFFF firefighting foam was awarded in June 1996 for extinguishing liquid hydrocarbon fires.

In the late 60’s, a series of major fuel fires happen on board US Navy ships causing extensive loss of life and damage:
(i) 1966: USS Oriskany – fire kills 44 sailors.
(ii) 1968: USS Forrestal – whilst on active service in the Gulf of Tonkin during the Vietnam War, malfunction and accidental firing of a fighter Zuni rocket on the flight deck of this super-carrier led to a catastrophic aviation fuel fire claiming the lives of 134 crew, injuring many more, destroying nearly 50 aircraft, doing $72 million worth of damage, and leaving the vessel unfit for active service.

(iii) 1969: USS Enterprise – a shipboard fire kills 28 sailors.

These major fires prompt the US Department of the Navy to mandate the use of the recently developed AFFF firefighting foam, which the 3M Company was manufacturing for the US military.

Perfluorocompounds had been successfully used to create AFFF, and 3M’s PFOS-based LightWater® and alcohol-resistant ATC® brands became the staple for liquid hydrocarbon fuel fires from the 1970s until May 2000 when the Company announced that it was phasing out PFOS-based chemistry on environmental grounds. AFFF had indeed conquered the world of firefighting and was seen for decades as the ultimate answer to extinguishing large hydrocarbon (oil and gasoline) fires both for military and civilian use especially by the aviation and petrochemical industries.

In the 70’s, an alternative technology was developed based on the telomerization process. This technology provided an alternative to the ECF process and introduced a new class perfluorochemicals on the market. Whereas the ECF process produced mainly PFOS contaminated with odd and even numbered homologues of PFOS such as PFHxS (~5-8 % w/w), perfluorohexane sulphonic acid, as well as branched chain isomers, telomerisation produced only even number linear alkyl carbon chains. The characteristic of fluorotelomer derivates is a perfluoroalkyl moiety linked by a dimethylene group -CH2-CH2- to a functional group which could be negatively (anionic), positively (cationic) or both negatively and positively charged (amphoteric).

Most modern fluorotelomer-based AFFF firefighting foams, known as ‘pure C6 foams’, are based on derivatives of 6:2 fluororelomer sulphonic acid (6:2FTS), or a thioether analogue, containing a C6 perfluoroakyl chain linked through -(CH2)2- to a charged functional group. 6:2FTS contains a C8 chain and its structure is shown below. Its similarity to PFOS is clear but the CH2 groups cause it to behave very differently in terms of its PBT profile. All perfluoroalkyl moieties or their breakdown products are extremely environmentally persistent (vP), but with differing bioaccumulation or toxic potential.

Figure 2. Structure of 6:2FTS

Early fluorotelomer foams, however, contained both 6:2FTS and often substantial amounts of 8:2FTS derivatives. This was a problem as the 8:2FTS could be degraded to a stable end product perfluoroctanoic acid or PFOA which had substantial toxicity. This problem has now been essentially resolved as a result of the industry PFOA Stewardship Program 2010-2015, with residual PFOA or its precursors reduced to less than 25 parts perbillion (ppb).

Figure 3. 8:2FTS breakdown to PFOA

From the 1970s to the late 1990s, many manufacturers of firefighting foam appeared in the market, developing and offering a wide range of different foams for end-users. These included Class B AFFF, AFFF-AR (alcohol resistant), film-forming-protein (FFFP) and fluoro-protein (FP) foams. Class A foams specifically intended for solid carbonaceous fires such as structural building or wildland (bush) fires were also developed in this period.

On 16 May 2000 the 3M Company abruptly announced the phasing-out of its activity in PFOS-based chemistry for producing fluorochemicals, affecting not only firefighting foams but also a wide range of domestic and commercial products. This announcement was justified on company responsibility for environment, as it was confirmed that the C8 perfluoroalkyl substances (PFAS) made using ECF technology posed a threat to the environment, with pollution that had spread worldwide affecting a wide range of environmental compartments as well as biota including man.
Over the next 2-3 years, the company had stopped all activities involving PFOS-based chemistry, with a total withdrawal from the firefighting foam market, replacing it with mitigated success by a shorter chain PFBS-based (perfluorobutyl sulphonate) chemistry. However, some production of PFOS and PFHxS derivatives using the ECF process did continue in both China and India.
With 3M’s phase-out of PFOS-chemistry and withdrawal from the firefighting foam market, other major manufacturers of PFAS fluorochemicals and firefighting foam stressed that they considered fluorotelomer chemistry was ’safe’ and indeed environmentally friendly as it had nothing to do with ECF chemistry and products could not contain either PFOS or PFOA. The firefighting foam market transitioned to AFFF products based on fluorotelomers over the next few years 2000-2010.

From 2002 onwards a lively and sometimes acrimonious debate took place between manufacturers of PFAS and AFFF – under the auspices of a trade association, the Fire Fighting Foam Coalition (FFFC), funded mainly by the fluorochemical industry – and independent manufacturers especially of nascent fluorine-free foams (F3), regulators and scientific experts from academia. This discussion gave rise to a series of international seminars, conferences as well as hundreds of publications in the peer-reviewed literature about the environmental consequences of substituting fluorotelomers for PFOS-based products. At this time the main international forum for discussing developments in firefighting foam technology turned out to be the Reebok series of foam conferences, held in Manchester and Bolton in the UK, 2002, 2004, 2007, 2009 and 2013.

Starting as early as 2002 a number of the smaller independent foam manufacturers started to offer first generation experimental Class B liquid hydrocarbon fluorine-free foams (F3) as more environmentally sustainable alternatives to PFAS -containing foams. During the following 10 years the debate raged on driven by published scientific studies which concluded that telomer chemistry posed a threat to the environment. Early telomer formulation were mixtures of 6:2 and 8:2 derivatives. The 8:2 material was shown to be a potential precursor for the generation of environmentally extremely persistent PFOA (perfluorooctanoic acid or C8) through breakdown, subsequently associated with long-term health effects. At the time this was vigorously contested by representatives advocating the fluorochemical industry attending Reebok conferences.
However, as a result of pressure from the US EPA many large feedstock manufacturers adopted the PFOA Stewardship Program 2010-2015 aimed at reducing the use of PFOA or its precursors. Improvements in purifying the fluorotelomer derivatives resulted in a reduction of PFOA related material to less than 25 ppb providing so-called ‘pure C6’ fluorotelomer derivatives. The Stewardship Program led to a change in foam formulations formerly containing C6/C8 fluorotelomers to a so-called ‘drop in’ replacement containing predominantly C6 fluorotelomer.
Unfortunately, this change was not as simple as it was supposed to be and foam manufacturers had to reformulate and increase the total fluorochemical content to achieve a similar performance compared with previous C6/C8 formulations. Unfortunately, end-users were not even made aware of this change!

Around the same time, scientific studies accumulated evidence that even hyper-pure C6 was NOT a suitable alternative, but a ‘regrettable substitution’ and the debate went to another level. 2015 marked a sea-change in the PFAS debate. The toxicity of PFOA was no longer denied by the fluorochemical industry or regulators and the issue was brought to the attention of the public by scientific journalists.

A series of public statements signed by scientists worldwide – the Helsingǿr Statement 2014, the Madrid Statement 2014 and the Zürich Statement 2018 – raised concerns about the continuing use of PFAS and as major planetary pollutants and their long-term impact on the environment. A major publication in 2020 raised the issue that all PFAS should be treated as a chemical class because of their common environmental problems rather than individual chemicals.

The United Nations Stockholm Convention and their Persistent Organic Pollutants Review Committee (POPRC) has added PFOS, PFHxS and PFOA to the appropriate Annexes banning or restricting use (2018-2022).

Countries such as Germany and Norway, or individual states such Queensland in Australia, have been at the forefront in regulating the use of PFAS, especially for highly dispersive use such as firefighting foams.

Some countries are not waiting for UN decisions to regulate the use of PFAS. In Europe, PFOS has been prohibited since 2011 and PFOA since 2018; current discussions aim to stop the use of all PFAS with C4 to C20 carbons completely with a deadline of 2025, in anticipation of these restrictions many industries are moving to fluorine-free technology. In the USA, change is being driven mainly by the cost of litigation with thousands of cases against the fluorochemical industry including foam manufacturers in the pipeline.

To be continued in Part 2

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About the authors : Dr Thierry BLUTEAU et Dr Roger A. Klein

Dr Thierry BLUTEAU
Managing Director
3F Americas – Panamá

Dr. Thierry BLUTEAU, French, studied at University of Paris XI, where he achieved a Master in Biochemistry and a PhD in Organic Chemistry.

In 1983, He is nominated as Professor of Biology at French Lycée in Montevideo in Uruguay for two years.

He starts to work in firefighting industry in 1992, where he is Technical Manager in Croda Fire Fighting Department.

6 years later, he funds the company Bio-EX, where he stands as Site Manager. He creates a range of firefighting foams and additives, and develops a wide network of international distributors, with presence in Asia, Australia, Africa and Latino America.`

In 2012, he keeps developing new foams independently in collaboration with LEIA Laboratories, and achieves the creation of two lines of innovative products : the firdt line is Smart Foam, foam products with no solvents and green profile. In 2020, a full line of FREGEN F3 is launched, fluoro-free products to be discovered on our website www.3fff.co.uk

Still active at R&D department in LEIA, he manages also our subsidiary 3F Américas in Panama City.

 

Dr. Roger A. Klein trained as a medical doctor and as a PhD physical chemist at the University of Cambridge. His academic research interests have covered tropical diseases, fundamental drug research, and more recently theoretical quantum chemistry (IUPAC Task Group on redefining hydrogen bonding) He has nearly 50 years experience advising and working with the Fire Service both in the UK and internationally, in areas that include hazardous materials (Hazmat and CBNRE) and decontamination issues, personal protective equipment (PPE), risk assessment and management, incident command and control, and the impact of fire service operations on the environment, having acted as Principal Scientific Adviser and Radiation Protection Adviser to Cambridgeshire Fire & Rescue Service until 2000. In the late 1990s he was asked by HM Fire Services Inspectorate to produce the first draft of UK guidance on risk assessment and management for the Emergency Services, which later became part of the Fire Service Manual. In 2002 he was involved in the McKinsey report on New York Fire Department (FDNY) operations at the 9/11 WTC incident in New York.

Following on from the 3M Company’s announcement on 16 May 2000 that it was withdrawing from PFOS-based chemistry he became heavily involved in the environmental chemistry of perfluorochemicals, especially as it affected the environment and human health through widespread contamination. In particular, he was concerned with the environmental impact of the dispersive use of firefighting foams, especially fluorosurfactant containing AFFF, and the transition to fluorine-free (F3) Class B foams. He has published extensively in the technical literature and co-organised a series of international seminars on the environmental impact of firefighting foams held at the Reebok Centre, Bolton, UK, in August 2002, December 2004, September 2007, July 2009 and March 2013, as well as the 1st Australian National Forum on Firefighting Foam held in Adelaide in 2011. More recently he has acted in an advisory capacity as a technical advisor to the Environment, Natural Resources and Rural Development Committee (ENRRDC) of the Parliament of Victoria (Australia) as part of the Inquiry into the legacy PFC contamination at the CFA Training College Fiskville, as well as accompanying the Committee on a study trip to Germany in December 2015.

He was also heavily involved in assisting the Queensland Government Department of Environment and Science in their development of a fire fighting foam management policy, including helping to co-organize a major conference held by the Department in Brisbane during February 2017. More recently he has been involved in presenting the case for fluorine-free firefighting (F3) foams as viable alternatives to AFFF as well as environmental and health issues concerning PFOS, PFOA and PFHxS to the UN Stockholm Convention Persistent Organic Pollutants Review Committee (POPRC-14) which met at the UN FAO Headquarters in Rome 17-21 September 2018, the ninth Convention of the Parties to the Stockholm Convention (COP-9) in Geneva 29 April-4 May 2019, and POPRC-15 also at FAO Headquarters in Rome 1-4 October 2019; acting as coordinator for the IPEN F3 Panel which produced a series of White Papers for the Committee and COP-9, which are now referenced by regulatory bodies. Formerly of the Universities of Cambridge and Bonn, and recently affiliated as a theoretical chemist to the Department of Chemistry, University of Wisconsin, Madison, since 2009 he has been Affiliated Research Faculty at the Christian Regenhard Center for Emergency Response Studies (RaCERS), John Jay College of Criminal Justice, CUNY New York.

In summary, since 2000 when the 3M Company announced withdrawing all PFOS-based chemistry, Roger Klein has been heavily involved in advising fire services, airports and industry, as well as collaborating with environmental regulators at national and international level, especially in Australasia (e.g., Australia, New Zealand, Singapore) and Northern Europe, in the control and remediation of PFAS environmental contamination. He assisted in the development of the 2016 Queensland foam management policy, now regarded as best-practice worldwide, and gave expert evidence to the Victorian Parliament’s Fiskville Inquiry 2015. He was also on the Advisory Board of a clinical study in Australia aimed at reducing blood PFAS levels in previously exposed firefighters, with the results published in April 2022 in the Journal of the American Medical Association (JAMA). He was previously a Member of the UK Institution of Fire Engineers, a Chartered Chemist and a Chartered Scientist; he is currently both a Fellow of the Royal Society of Chemistry and a Fellow of the International Union of Pure and Applied Chemistry (IUPAC); he now works as an independent scientific consultant.

Contact details:
Dr. Roger A. Klein, tel: +44 1223 306 846 mob: +44 07555 545 070 email: rogeraklein@yahoo.co.uk

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