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B.1 Laitinen

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  • 1. Fire Fighters’ multiple exposure to perfluoroalkyl acids (PFC) and 2-butoxyethanol present in AFFFs J. Laitinena, J. Koponenb, J. Koikkalainenc, H. Kivirantab Finnish Institute of Occupational Health, Neulaniementie 4, FI-70101 Kuopio, Finland a National Institute for Health and Welfare, Neulaniementie 4, FI-70101 Kuopio, Finland b University of Eastern Finland, Yliopistoranta 1, FI-70211 Kuopio, Finland c 1 © Finnish Institute of Occupational Health – www.ttl.fi
  • 2. Topics of presentation 1. Introduction 2. Aims of the study 3. Materials 4. Methods 5. Results 6. Conclusion 2 © Finnish Institute of Occupational Health – www.ttl.fi
  • 3. 1. Introduction • Aqueous film forming foams (AFFFs) are used to extinguish hydrocarbonfuel and chemical solvent fires • Its role is to cool the fire and to coat the fuel, preventing its contact with oxygen • This can happened with help of fluorinated (F) and hydrocarbon surfactants (S), they form a film of aqueous solution covered from both sides by monolayers of mixed surfactants 3 © Finnish Institute of Occupational Health – www.ttl.fi
  • 4. 1. Introduction • Most common components in AFFFs concentrates are solvents (2-butoxyethanol or 2-(2-butoxyethoxy)ethanol) which are required for solubilisation of surfactants and as anti-freesing agents, and foam stabilizers. • AFFFs might contain also fluorinated (PFAScompounds or fluorotelomers) and hydrocarbon surfactants (sodium alkyl sulfate), which are critical for the foaming and vapour-sealant properties and stability of the foam. • Foams will also contain small amounts chemicals that are used as buffers, corrosion inhibitors, polymeric stabilisers, foam thickeners and agents enhancing foam film spreading 4 © Finnish Institute of Occupational Health – www.ttl.fi
  • 5. 1. Introduction • PFC-compounds are bioaccumulative and very persistent in the environment • PFC compound are also suspected to be hormone disrupters • PFOA is suspected to be associated with increased risk of chronic kidney disease • critical target organs of alkoxyalcohols are CNS, liver, blood and also kidneys 5 © Finnish Institute of Occupational Health – www.ttl.fi
  • 6. 2. Aims of the study • To analyse the profile of PF compounds in used foam • To assess fire fighters’ exposure to foam • To evaluate eight commercially available AFFFs from the occupational and environmental hygienic perspective 6 © Finnish Institute of Occupational Health – www.ttl.fi
  • 7. 3. Materials • This study was carried out during the training of suppression of liquid fire in aircraft accident simulation. • To the each trainings participated eight firefighters and their smoke diving session together took about 60 minutes in each training • Sthamex AFFF 3% -foam was used for suppression of jet propulsion fuel fire • Foam contained perfluorinated surfactants and as anti-freezing agents was used 2-butoxyethanol • The profile of PFAS- compounds was confirmed with LC-MS/MS – analyses from foam liquid • Fire fighters’ hobbies, dietary intake, work history was recorded by questionnaire designed by National Institute for Health and Health – www.ttl.fi Welfare. © Finnish Institute of Occupational 7
  • 8. 3. Materials • Suppression of jet propulsion fuel fire • Rescuing survivals from crashed airplane • Cleaning environment after training • Maintenance of used fire hose, fire foam truck and personal protective equipments 8 © Finnish Institute of Occupational Health – www.ttl.fi
  • 9. 4. Methods • Fire fighters’ exposure to PFC-compounds was evaluated by serum samples taken before first training and two weeks after three training sessions (3.3., 31.3. and 6.5.). • All samples were analysed by LC-MS/MS in National Institute for Health and Welfare • Following PFAS-compounds was analysed from serum: perfluorohexanoic acid (PFHxA),perfluoroheptanoic acid (PFHpA), perfluoro-octanoic acid (PFOA),perfluorononanoic acid (PFNA), perfluorodekanoic acid (PFDA), perfluoroundecanoic acid(PFUnA), perfluorododekanoic acid (PFDoA), perfluorotridekaanoic acid (PFTrA), perfluorotetradekanoic acid (PFTeA), perfluorohexane sulfonic acid (PFHxS), perfluoroheptane sulfonic acid (PFHpS), perfluoro-octane sulfonic acid (PFOS), perfluorodecane sulfonic acid (PFDS) 9 © Finnish Institute of Occupational Health – www.ttl.fi/en
  • 10. 4. Methods • • • • Fire fighters’ exposure to 2-butoxyethanol was analysed by biomonitoring of urinary 2butoxyacetic acid (BAA). Urine samples was taken before exposure and immediately after exposure. Analyses were done by GC-FID in Finnish Institute of Occupational Health Eight commercially available AFFFs was evaluated in literature study from the occupational hygienic perspective. Evaluated foams were: • Conventional foams: Sthamex AFFF 3 % and Afrofilm AFFF 3 % • Alcohol resistant AR-foams: Moussol APS 3 % and Arctic foam 602 ATC 3-6 % • PFAS-free and AR-foams: Re-healing foam RF3X6 ATC 3-6 % and Bio Ex Ecopol 3X3//3X6 • Training foam: Solberg TF5X 10 © Finnish Institute of Occupational Health – www.ttl.fi/en
  • 11. 5. Results –Profile of PFC -compounds in Sthamex AFFF 3 % -liquid and in fire fighters’ serum • • 11 We able to find from fire fighters’ serum four of the seven most important PFAS-compounds in Sthamex AFFF -liquid During the surveillence period the proportion of perfluorohexane sulfonic acid showed the highest increase in fire fighters’ serum © Finnish Institute of Occupational Health – www.ttl.fi
  • 12. 5. RESULTS: Fire fighters’ average excretion of PFOA, PFNA, PFHxS and PFOS Increase 7.2 % Increase 10 % Increase 19 % Increase 4.7 % 12 © Finnish Institute of Occupational Health – www.ttl.fi
  • 13. 5. RESULTS -Fire fighters’ exposure to 2-butoxyethanol • The average concentrations of 2butoxyacetic acid exceeded the reference limit of the general population in second and third training sessions. • This might indicate that dermal exposure play certain role in fire fighters’ training in suppression of jet propulsion fuel fire 13 © Finnish Institute of Occupational Health – www.ttl.fi
  • 14. 5. RESULTS -Effects of dietary upatake, hobbies and work history to PFC –excretion, the best fire fighting foam for future needs • We did not able to find correlation between measured serum PFAS concentrations and recorded information about fire fighters’ dietary intake, hobbies and work history • The best fire fighting foam was Bio Ex Ecopol 3X3//3X6. • It has enough low freesing point, so it working also in cold environments. • It’s surfactants were PFC-free • It fulfilled future requirements of biofuels concerning alcohol resistance 14 © Finnish Institute of Occupational Health – www.ttl.fi
  • 15. 6. CONCLUSIONS • Fire fighters’ average excretion levels of PFAS compounds were higher than average excretion of general population in Finland (PFOS 7 ng/ml, PFOA 3 ng/ml, PFHxS 1 ng/ml and PFNA 1 ng/ml.) • The excretion of PFOA, PFOS, PFHxS and PFNA increased during the training session, which reflects slight accumulation of PFAS-compounds during training period. • The excretion of PFHxS showed the highest increase during training sessions. So it seemed to be the best indicator of exposure to PHAS-compounds during usage of Sthamex – foam. • Fire fighters’ average excretion of 2-butoxyacetic acid exceeded the limit for general population, which also indicate slight exposure to 2-butoxyethanol • In the selection of AFFFs for liquid fires, non-fluorine based products should be favoured in the future. Alcohol resistance properties of foams must also be taken into account due to the increased use of biofuels. Bio Ex Ecopol 3X3//3X6 fulfilled all these requirements 15 © Finnish Institute of Occupational Health – www.ttl.fi/en
  • 16. Thank you for your attention ! Thank you for your attention ! 16 © Finnish Institute of Occupational Health – www.ttl.fi/en